2-quinolinone derivatives

ABSTRACT

The present invention relates to novel 2-quinolinone derivanves of the following general formula(I) useful in agriculture, especially as fungicides but also as insecticides and miticides. ##STR1## wherein, R 1 , R 2 , R 3  and R 4  are independently hydrogen, halogen, C 1  -C 10  alkyl, branched C c  -C 4  alkyl, C 1  -C 3  haloalkyl, C 1  -C 3  alkoxy, C 1  -C 3  haloalkoxy, C 1  -C 3  alkylthio, C 1  -C 3  haloallcylthio, NO 2 , CN, alkoxy carbonyl, phenyl, substituted phenyl, phenoxy, substituted phenoxy, benzenesulfonyl, benzyi, substituted benzyl or morpholine; 
     R 5  is C 1  -C 6  alkyl, branched C 3  -C 6  alkyl, C 3  -C 6  cycloalkyl, phenyl, substituted phenyl, benzyl or phenylthio methyl: and 
     X is S(O)nR 6 , OR 9  or NAB: 
     wherein. 
     n is 0 or 1; 
     R 6 , R 9 , A and B are defined within the description.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to novel 2-quinolinone derivatives of the following general fomula(I) useful in agriculture, especially as fungicides but also as insecticides and miticides. ##STR2## wherein, R₁, R₂, R₃ and R₄ are independently hydrogen, halogen, C₁ -C₁₀ alkyl, branched C₃ -C₄ alkyl, C₁ -C₃ haloalkyl, C₁ -C₈ alkoxy, C₁ -C₃ haloalkoxy, C₁ -C₃ alkylthio, C₁ -C₃ haloalkylthio, NO₂, CN, alkoxy carbonyl, phcnyl, substituted phenyl, phenoxy, substituted phenozxy, benzenesulfonyl, benzyl, substituted benzyl or morpholine;

R₅ is C₁ -C₆ alkyl, branched C₃ -C₆ alkyl. C₃ -C₆ cycloalkyl, phenyl, substituted phenyl, benzyl or phenylthio methyl; and

X is S(O)nR₆, OR₉ or NAB:

wherein,

n is 0 or 1:

R₆ is R₇ or R₈, and then R₇ is C₁ -C₆ alkyl, branched C₃ -C₆ alkyl, C₁ -C₃ haloalkyl, benzyl or substituted benzyl, and R₈ is phenyl, substituted phenyl, benzyl or substituted benzyl;

R₉ is C₂ -C₅ alkyl, branched C₃ -C₄ alkyl, C₅ -C₆ cycloalkyl, phenyl or substituted phenyl;

A and B are combined together to fonn a saturated or unsaturated 5 or 6-membered cyclic ring or fused ring, optionally including a hetero atom selected from O or N, or optionally substituted with C₁ -C₃ alkyl or carbocyclic ring including N atom, or one of A and B is H and the other is R₁₀ or Z--Ar; and then,

R₁₀ is saturated or unsaturated C₁ -C₁₀ alkyl, branched C₃ -C₈ alkyl or C₃ -C₆ cycloalkyl optionally including a hetero atom selected from O, S or N or optionally substituted with C₁ -C₃ alkyl or alkoxycarbonyl, C₁ -C₃ haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl, phenyl, substituted phenyl, pyridyl, substituted pyridyl, pyrimidyl, or substituted pyrimidyl;

Z is C₁ -C₄ alkyl chain, optionally containing cyclopropylene ring, or optionally substituted with C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ hydroxyalkyl or or phenyl; and

Ar is C₃ -C₆ cycloalkyl, optionally including a nitrogen atom, or pyridyl, substituted pyridyl, or a phenyl group of the following formula (II) ##STR3## wherein, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are independently H, halogen, C₁ -C₆ alkyl, branched C₃ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, phenyl, phenoxy, phenylthio, CN, NO₂, NH₂, or SO₂ NH₂.

Description of the Prior Art

There is an acute need for new fungicities, insecticides, and miticides, because target pathogens are rapidly developing resistance to currently used pesticides. The development of resistance to some of the fungicides in current use, such as the triazoles, the benzimidazoles, the acylalanines, and the organophosphates and the insecticides, such as the carbamates, the organophosphates, and the pyrethroids, is well known. Therefore a need exists for new fungitides, insecticides, and miticides.

SUMMARY OF THE INVENTION

The present invention relates to novel 2-quinolinone derivatives having the above general formula(I), which have fungicidal and insecticidal activity.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of the general formula(I) according to the present invention can be prepared by reactions as described herein below.

The compounds(Ia) of general formula(I) wherein X is SR₆, and then R₆ is R₇, can be made by thermally cyclizing compounds of following formula(III), and the compounds(Ib) of general formula(I) wherein X is SOR₆, and then R₆ is R₇, may be prepared by oxidizing the corresponding compounds(Ia) using a conventional oxidation procedure. ##STR4## wherein, R₁, R₂, R₃, R₄, R₅ and R₇ are as previously defined.

The above reaction may be camed out without solvent or under the presence of solvent, for example, hydrocarbon solvents such as paraffin oil, benzenes such as xylene and dichlorobenzene, amides such as dimethyl formamide and dimethyl acetamide, anilines such as N,N-dimethylaniline and N,N-diethyl aniline, ethers such as diphenyl ether, or a mixture of them.

The cyclizing reaction is camed out at 140°˜250° C., preferably 160°˜200° C. If the temperature is lower than 140° C., the reaction rate is very slow, and ff higher than 250° C., it is attended with the severe evolution of mercaptan(R₇ SH) as a by-product.

Alteratively, the compounds(Ia') of general formula(I) wherein X is SR₆, and then R₆ is R₈, can be manufactured by reacting the compounds of above formula(Ib) with thiol of following formula(IV), and the compounds(Ib') wherein X is SOR₆, and then R₆ is R₈, can be prepared by oxidizing the corresponding compounds(Ia') using a conventional oxidation procedure. ##STR5## wherein, R₁, R₂, R₃, R₄, R₅ and R₈ are as previously defined.

The compounds of above formula(Ia') can be prepared by the substitution reaction heating 4-alkylsulfoxyquinolinone of the above formula(Ib) and thiophenol derivative of the above formula(IV) without solvent or under the presence of solvent, and then the solvent as the above, e.g. hydrocarbons, benzenes, amides, anilines, ethers, or their mixture, may be used.

The substitution reaction is carried out at 100°˜250° C., preferably 160°˜200° C. If the temperature is lower than 100° C., the reacting rate is very slow, and if higher than 250° C., the yields are very low.

The compounds(when n in X of formula(I) is 1 ) of the formula(Ib) and (Ib') can be prepared by oxidation of the compounds(when n in X of formula(I) is 0 ) of the formula(Ia) and (Ia') using a conventional oxidants, for example, organic or inorganic peroxy compounds such as hydrogen peroxide, potassium peroxymonosulfate, tertiary butyl hydroperoxide, m-chloro peroxybenzoic acid, peroxyacetic acid, and magnesium monoperoxyphthalate.

And then, solvent may be used as followings; water; hydrocarbon halide such as dichloromethane, chloroform, carbon tetrachloride, and chlorobenzene; aliphatic acid such as acetic acid and propionic acid; or alcohols such as methyl alcohol, ethyl alcohol, etc.

The reaction may be carried out at 0°˜130° C., preferably 20°˜60° C., and then if the temperature is lower than 0° C., the reaction rate is very slow, and if higher than 130° C., the used solvent may be boiled over.

The amount of used oxidant may be usefully 1.2 fold or more with the used compound of the formula(Ia) or (Ia'), but it is not limited specially.

The quinolinone derivatives of the formula(Ia) and (Ib') and sulfoxy-2-quinolinone derivatives may be optionally recrystallized or purified by chromatography.

The compounds(Ic) of general formula(I) wherein X is OR₉ and then R₉ is methyl can be prepared by the known process described in J. Org. Chem. Vol. 31, P1276-1278(1966) or J. Org. Chem. Vol. 34, P2183-2187(1969) by J. W. Huffman and J. H. Cecil. Especially, 3-isobutyryl-4-methoxy-(2H)quinolinone, 3-isobutyryl- 4,8-dimethoxy-2(1H)-quinolinone, 3-isovaleryl-4-methoxy-2(1H)-quinolinone or 3-isovaleryl-4,8-dimethoxy-2(1H)-quinolinone were prepared in 14˜18% yields by reacting the corresponding 3-acyl-4-hydroxy-2(1H)-quinolinone with diazomethane, and separation of the resulted mixture of 2(1H)-quinolinone, 1-methyl-2(1H)-quinolinone and other products as using liquid chromatography.

In this invention, the compounds(Ic) of general formula(I) wherein X is OR₉ were made by condensing the compounds of formula(Ib) with an alcohol of the formula(V). ##STR6## wherein, R₁, R₂, R₃, R₄, R₅ and R₉ are as previously defined.

Also, the above compound(Ic) may be prepared by substitution of alcohols(R₉ OH) under heating without solvent or under the presence of a solvent, or directly using alcohol as a solvent, and then the base may be used or not.

The used solvent may be, excepting alcohol used as a reactant, dimethyl formamide, acetonitrile, dioxane, benzene, toluene, xylene, tetrahydrofuran, hexane, heptane, or a mixture of them. The base may be, for example, pyridine, triethylamine, N,N-dialkylaniline, alkalimetal hydroxide, alkalimetal carbonate, metal hydride, etc.

The substitution reaction is carded out at boiling point of solvent or between room temperature and 200° C., preferably at 50°˜120° C.

The compounds(Id) of general formula(l) wherein X is NAB and then NAB is NMe₂ can be prepared by the known process described in Helv. Chim. Acta., Vol. 52, P 264˜2657(1969) by H. J. Gais, K. Hafiner and M. Neuenschwander. Especially, 3-acetyl-4,8- (dimethylamino)- 2(1H)-quinolinone may be obtained by reaction of phenylisocyanate and 1-dimethytamino-3-oxo-1-butylene according to [4+2]cycloaddition.

In this invention, the compounds(Id) of general formula(I) wherein X is NAB were prepared by condensing the compounds of formula(Ib) with the amines of the formula(VI) ##STR7## wherein, R₁, R₂, R₃, R₄, R₅, A and B are as previously defined.

The above compound(Id) a be prepared by reacting 4-alkylsulfoxy-2-quinolinone of the above formula(Ib) with an amine compound of the following formula(VI) under the presence of inert solvent.

When the amine compound of formula(VI) is acid salt, an acid remover for example, trialkylamines (such as triethylamine), potassium carbonate, inorganic base (such as sodium hydroxide), may be used, as adding 1˜2 equivalents, and thereafter acid adding salt of amine compound is added.

An inert solvent used in the present invention may be, for example, ethers such as diethylether, diisopropyl ether, tetrahydrofuran, dioxane, diphenylether, etc.; hydrocarbons such as benzene, toluene, xylene, ligroine, etc.; hydrocarbon halides such as dichloroethane, chloroform, carbon tetrachloride, etc.; esters such as ethyl acetate, ethyl propionate, etc.; chlorobenzenes such as monochlorobenzene, dichlorobenzene, etc.; aprotic polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, etc., but the above reaction may be carried out without solvent.

According to the present invention, pyridine or trialkylamine may be used as two purposes of a base and a solvent. The reaction can be carried out at 0°˜260° C., preferably between room temperature and boling point of the solvent, and then the reacting time is preferable of 0.5˜8 hr but it is affected by the reaction temperature.

As a result of the reaction, when the amine compound of formula(VI) being not acid adding salt is used, the crude product is obtained by evaporating the solvent under the reduced pressure.

But, when the amine compound of formula(VI) being acid adding salt is used, the crude product may be obtained by following process; the solvent is evaporated under the reduced pressure; water is added to dissolve the salts; the resulting mixture is extracted with water-insoluble organic solvent such as methylenechloride, chloroform, ethyl acetate, etc.; and the organic layer is evaporated under the reduced pressure to afford the crude product.

The obtained 2-quinolinone derivatives of formula(Id) may be purified by column chromatography or recrystallized by the following solvent; alcohol solvent such as methanol, ethanol, etc.; ester of organic acid such as ethyl acetate, methyl acetate, etc.; hydrocarbon solvent such as pentane, hexane, etc.; ether such as ethylether, tetrahydrofuran, etc.

On the other hand, the starting material used in the present invention, ketene dithio acetal α-anilide of the formula(IH), can be prepared from β-ketoanilide by the following reaction process ##STR8## wherein, R₁, R₂, R₃, R₄, R₅ and R₇ is respectively as the above defined, Y is chlorine, bromine, iodine, or alkyl or arylsulfonate.

The compounds according to the present invention have highly curative and protective fung icidal activity for plant germs of widely spectrum as followings; for example, rice blast (Piricularia oryzae), rice sheath blight (Rhizoctonia solani), cucumber gray mold (Botrytis cinerea), cucumber powdery mildew (Sphaerotheca fuliginea), cucumber downy mildew (Pseudoperonospora cubensis), grape downy mildew (Plasmopora viticola), tomato late blight (Phytophthora infestans), rice brown spot (Cochliobolus miyabeanus), peanut brown leaf spot (Cercospora arachidicola), barley powdery mildew (Erysiphe graminis), wheat leaf rust (Puccinia recondita), wheat stem rust (Puccinis graminis), and wheat eye spot (Pseudocercosporella herpotrichoides). Also, the compounds according to the present invention have highly insecticidal activity for noxious insects, for example, house fly, mosquito, cockroach and agricultral insects, for example, Hemiptera such as small brown plant hopper (Laodephax striatellus Fallen), brown plant hopper (Nilaparvata lugens Stail), white-backed rice plant hopper (Sogatella furcifera Horvath), green rice leaf hopper (Nephotettix cincticeps Uhler), greenhouse white fly (Trialeurodes vaporariorum Westwood), and green peach aphid (Myzus persicae Sulzer); Lepidoptera such as apple leafminer (Phyllonorycter ringoniella Matsumura), diamond-back moth (Plutella xylostella Curtis), rice armyworm (Pseuclaletia separata Walker), cabbage armyworm (Mamestra brassicae Linnaeus), tobacco cutworm (Spodoptera litura Fablicius), and common cabbage worm(Pieris rapae Linnaeus); Coleoptera such as rice leaf beetle (Oulema oryzae Kuiwayarna), and rice-plant weevil rice curculio (Echinocnemus squameus Billbery).

Useful formulations of the compounds of formula(I) can be prepared by mixing the compounds of active ingredient of about 0.01˜90 weight % with proper solid or liquid carrier and supporters such as surfactant, diluent, spreader, synergist, adhesive, dispersant, etc.

The used solid carrier may be usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates, and liquid carrier may be water, alcohol, methanol, ethanol, acetone, dimethylformamide, ether, benzene, xylene, toluene, naphtha, etc.

Suffactant may be nonionic suffactant(e.g., polyoxy ethylene alkylphenylether and poly oxyethylene fatty acid ester), artionic suffactant(alkyl benzenesulfonic acid, lignine sulfonate and dinaphthalene methane sulfonate), etc. Polyvinylalcohol, CMC, gum arabic, etc. may be used as adhesive.

The fungicidal and insecticidal compositions using the compounds of the present invention may be manufactured as formulation such as powder, wettable powder, granules, emulsifiable concentrates, suspensions, solution, fumigant, gas phase, etc., and thekr fonnulations were used in earth, agriculural products, seedling, seeds, etc.

For example, emulsifiable concentrates or solution may be prepaxed by uniformly dissolving the compound of formula(I) with hydrocarbon, acetone or alcohol and surfactant.

Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, inert carder and surfactants.

The combinations including the compounds according to the present invention may be used by mixing with agricultural chemicals such as insecticides, fungicides, herbicides, plant growth regulants, miticides, etc.

Especially, since the known fungicides have resistance, the compounds of formula(I) of more than 1 weight % may be used with the known fungicides including following compounds;

1) N-substituted azoles, for example, prochloraz, triademefon, and flusilazol;

2) pyrimidines, such as fenarimol and nuarimol;

3) morpholines, such as fenpropimorph and tridemorph;

4) piperazines, such as triforine;

5) pyridines, such as pyrifenox;

6) dithiocarbamates, such as maneb and mancozeb;

7) phthalimides, such as captafol;

8) isophthalonitriles, such as chlorothalonil;

9) dicarboximides, such as iprodione;

10) benzimidazoles, such as benomyl and carbendazim;

11) 2-aminopyrimidines, such as ethirimol;

12) carboxamides, such as carboxin; and

13) dinitrophenols, such as dinocap.

The fungicide combinations of the invention contain at least 1%, generally 20˜80% by weight of a compound of formula (1).

The compounds of said formula(D according to the present invention specify as the following Tables 1˜4;

                                      TABLE 1                                      __________________________________________________________________________     4-alkyl or arylthio-2-quinolinone(I-a, I-a') and 4-alkyl or                    arylsulfoxy-2-quinolinone(I-b, I-b')                                            ##STR9##                                                                      Comp. No.                                                                            R.sub.1                                                                           R.sub.2                                                                               R.sub.3                                                                           R.sub.4                                                                             R.sub.5                                                                              R.sub.5     n m.p. (°C.)                  __________________________________________________________________________     1     H  H      H  H    CH.sub.3                                                                             CH.sub.3    0 226-231                            2     "  "      OCH.sub.3                                                                         "    "     "           " 194-199                            3     "  "      H  Cl   "     "           " 135-137                            4     Cl "      "  Cl   "     "           " 171-175                            5     H  OCH.sub.3                                                                             "  H    "     "           " 232-233                            6     "  H      F  "    "     "           " 225-227                            7     "  F      H  "    "     "           " 233-235                            8     "  H      "  F    "     "           " 139-141                            9     "  "      "  Cl   n-C.sub.3 H.sub.7                                                                    "           " 110-112                            10    "  "      "  "    C.sub.2 H.sub.5                                                                      "           " 130-131                            11    "  "      "  CH.sub.3                                                                            CH.sub.3                                                                             "           " 93-94                              12    "  "      "  Cl   C.sub.6 H.sub.5                                                                      "           " 199-202                            13    "  Cl     "  CF.sub.3                                                                            CH.sub.3                                                                             "           " 118-121                            14    "  H      "  H    C.sub.6 H.sub.5                                                                      "           " 265-268                            15    "  "      "  F    CH.sub.3                                                                              ##STR10##  " 109-111                            16    H  H      H  CO.sub.2 CH.sub.3                                                                   CH.sub.3                                                                             CH.sub.3    0 233-234                            17    "  Cl     "  H    "     "           " 197-198                            18    "  H      "  NO.sub.2                                                                            "     "           " 184-185                            19    NO.sub.2                                                                          "      "  Cl   "     "           " 201-203                            20    H  NO.sub.2                                                                              "  H    "     "           " 222-226                            21    "  Cl     NO.sub.2                                                                          H    "     "           " 281-283                            22    "  H      H  CN   "     "           " 171-173                            23    "  Cl     "  CF.sub.3                                                                            CH.sub.3                                                                              ##STR11##  " 110-113                            24    "  t-Bu   "  H    "     CH.sub.3    " 154-156                            25    "  H      "  SO.sub.2 C.sub.6 H.sub.5                                                            "     "           " 211-213                            26    NO.sub.2                                                                          "      "  F    "     "           " >260                               27    Cl Cl     Cl Cl   "     "           " 188-191                            28    H  CF.sub.3                                                                              H  H    "     "           " 151-153                            29    "  H      "  CF.sub.3                                                                            "     "           " 98-99                              30    "  Br     "  "    "     "           " 139-141                            31    "  H      "  SCF.sub.3                                                                           CClFH "           " 127-129                            32    "  OC.sub.5 H.sub.11 -n                                                                  "  H    "     "           " 134-137                            33    "  F      "  CF.sub.3                                                                            "     "           " 138-140                            34    "  H      F  "    "     "           " 164-166                            35    "  Br     CF.sub.3                                                                          H    "     "           " 138-140                            36    "  Cl     "  "    "     "           " 149-151                            37    "  n-C.sub.6 H.sub.13                                                                    H  "    "     "           " 94-98                              38    "  F      F  F    "     "           " 132-134                            39    "  Cl     H  CF.sub.3                                                                            "                                                                                     ##STR12##  " 143-144                            40    "  F      Cl H    "     CH.sub.3    " 141-143                            41    CF.sub.3                                                                          H      H  Cl   "     "           " 206-208                            42    H  Cl     H  CH.sub.3                                                                            CH.sub.3                                                                             CH.sub.3    0 164-166                            43    "  H      "  C.sub.2 H.sub.5                                                                     "     "           " 87-88                              44    "  "      "  "    "                                                                                     ##STR13##  " 116-117                            45    "  CF.sub.3                                                                              Cl H    "     CH.sub.3    " 149-151                            46    "  H      "  Cl   "     "           " 143-144                            47    "  t-Bu   H  H    "                                                                                     ##STR14##  " 118-120                            48    "  H      "  CN   "                                                                                     ##STR15##  " 115-116                            49    "  CF.sub.3                                                                              "  NO.sub.2                                                                            "     CH.sub.3    " 156-157                            50    H  Cl     Cl H    CH.sub.3                                                                             CH.sub.3    " 150-152                            51    Cl "      H  "    "     "           " 223-225                            52    H  H      CF.sub.3                                                                          "    "     "           " 135-138                            53    "  Cl     H  Cl   "                                                                                     ##STR16##  " 215-217                            54    "  "      "  CF.sub.3                                                                            "                                                                                     ##STR17##  " 179-181                            55    Cl H      "  Cl   "                                                                                     ##STR18##  " 184-185                            56    H  Cl     "  "    "                                                                                     ##STR19##  " 101-102                            57    "  "      "  CH.sub.3                                                                            "                                                                                     ##STR20##  " 162-163                            58    "  "      "  "    "                                                                                     ##STR21##  " 158-160                            59    Cl H      "  "    "     CH.sub.3    " 164-165                            60    CH.sub.3                                                                          "      CH.sub.3                                                                          H    "     "           " 151-153                            61    Cl "      H  Cl   "     n-C.sub.4 H.sub.9                                                                          " 105-106                            62    H  "      "  i-C.sub.3 H.sub.7                                                                   "     CH.sub.3    " 101-102                            63    Cl "      Cl H    "     "           " 165-166                            64    H  "      H  CF.sub.3                                                                            "     n-C.sub.4 H.sub.9                                                                          " 91-93                              65    "  "      "  C.sub.6 H.sub.5                                                                     "     CH.sub.3    " 131-132                            66    "  "      "  "    "     n-C.sub.4 H.sub.9                                                                          " 84-87                              67    "  "      "  "    "                                                                                     ##STR22##  " 123-126                            68    H  H      H  C.sub.6 H.sub.5                                                                     CH.sub.3                                                                              ##STR23##  0 82-83                              69    CH.sub.3                                                                          "      "  Cl   "     CH.sub.3    " 159-161                            70    H  CH.sub.3                                                                              "  CH.sub.3                                                                            "                                                                                     ##STR24##  " 138-139                            71    Cl H      "  Cl   "                                                                                     ##STR25##  " 155-156                            72    H  H      H  i-C.sub.3 H.sub.7                                                                   CH.sub.3                                                                              ##STR26##  " 117-119                            73    "  "      "  "    "     n-C.sub.4 H.sub.9                                                                          " 44-45                              74    "  "      "  CH.sub.2 C.sub.6 H.sub.5                                                            "     CH.sub.3    " 135-137                            75    "  Cl     "  CF.sub.3                                                                            "     C.sub.2 H.sub.5                                                                            " 87-89                              76    "  H      "  n-C.sub.3 H.sub.7                                                                   "     CH.sub.3    " 73-74                              77    "  "      Cl CH.sub.3                                                                            "     CH.sub.3    " 132-135                            78    "  Cl     H  CF.sub.3                                                                            "     n-C.sub.6 H.sub.13                                                                         " 66-68                              79    "  CH.sub.3                                                                              Cl H    "     CH.sub.3    " 143-145                            80    Cl "      H  "    "     "           " 156-158                            81    H  H      "  CH.sub.2 C.sub.6 H.sub.5                                                            "     n-C.sub.4 H.sub.9                                                                          " 80-81                              82    "  "      "  "    "     i-C.sub.5 H.sub.11                                                                         " 66-67                              83    "  Cl     "  F    "     CH.sub.3    " 153-156                            84    "  NO.sub.2                                                                              "  Cl   "     "           " 197-198                            85    CH.sub.3                                                                          H      "  "    "     "           " 161-162                            86    H  F      "  "    "     "           " 146-147                            87    CF.sub.3                                                                          H      "  OCH.sub.3                                                                           "     "           " 259-261                            88    H  OCH.sub.3                                                                             "  NO.sub.2                                                                            "     "           " 175-179                            89    "  H      Cl Cl   "     C.sub.2 H.sub.5                                                                            " 118-120                            90    "  "      H  CH.sub.3                                                                            "     CH.sub.3    1 204-206                            91    "  "      "  Cl   "     "           " 219-220                            92    "  OCH.sub.3                                                                             "  H    "     "           " 220                                93    Cl H      "  Cl   "     "           " 240-242                            94    H  Cl     H  H    CH.sub.3                                                                             CH.sub.3    1 235-238                            95    "  H      "  Cl   C.sub.6 H.sub.5                                                                      "           " 221-223                            96    "  F      "  H    CH.sub.3                                                                             "           " 242-244                            97    "  H      "  F    "     "           " 190-193                            98    "  Cl     "  CF.sub.3                                                                            "     "           " 196-198                            99    "  H      "  H    C.sub.6 H.sub.5                                                                      "           " 239-241                            100   "  H      H  F    "                                                                                     ##STR27##  " 218-220                            101   "  H      H  CO.sub.2 CH.sub.3                                                                   CH.sub.3                                                                             CH.sub.3    " 232-234                            102   "  "      "  CF.sub.3                                                                            "     "           " 211-213                            103   "  "      "  SO.sub.2 C.sub.6 H.sub.5                                                            "     "           " 209-211                            104   "  "      "  CN   "     "           " 224-226                            105   NO.sub.2                                                                          "      "  F    "     "           " 246-248                            106   CF.sub.3                                                                          "      "  Cl   "     "           " 233-235                            107   H  F      Cl H    "     "           " 245-247                            108   "  Cl     H  Cl   "     "           " 214-216                            109   NO.sub.2                                                                          H      "  "    "     "           " 247-249                            110   H  Cl     "  CH.sub.3                                                                            "     "           " 220-222                            111   "  H      "  C.sub.2 H.sub.5                                                                     "     "           " 210-211                            112   "  "      Cl Cl   "     "           " 200-202                            113   "  CF.sub.3                                                                              H  NO.sub.2                                                                            "     "           " 164-167                            114   "  H      CF.sub.3                                                                          H    "     "           " 203-207                            115   "  Cl     H  CF.sub.3                                                                            "                                                                                     ##STR28##  " 198-199                            116   Cl H      "  Cl   "     "           " 177-180                            117   H  CF.sub.3                                                                              "  H    "     CH.sub.3    " 228-230                            118   "  Cl     "  CH.sub.3                                                                            "                                                                                     ##STR29##  " 202-203                            119   "  "      "  "    "                                                                                     ##STR30##  " 164-169                            120   Cl H      H  CH.sub.3                                                                            CH.sub.3                                                                             CH.sub.3    1 243-244                            121   CH.sub.3                                                                          "      CH.sub.3                                                                          H    "     "           " 229-231                            122   Cl "      H  Cl   "     n-C.sub.4 H.sub.9                                                                          " 172-173                            123   Cl "      Cl H    "     "           " 211-213                            124   Cl "      Cl H    "     "           " 250-252                            125   CF.sub.3                                                                          "      CF.sub.3                                                                          "    "     "           " 230-233                            126   H  "      H  C.sub.6 H.sub.5                                                                     CH.sub.3                                                                             CH.sub.3    " 267-270                            127   "  Cl     "  CF.sub.3                                                                            "     n-C.sub.4 H.sub.9                                                                          " 123-125                            128   NO.sub.2                                                                          H      "  OCH.sub.3                                                                           "     CH.sub.3    " >260                               129   H  "      "  C.sub.6 H.sub.5                                                                     "     n-C.sub.4 H.sub.9                                                                          " 147-150                            130   "  "      "  "    "                                                                                     ##STR31##  " 151-154                            131   "  "      "  "    "                                                                                     ##STR32##  " 209-211                            132   "  "      "  i-C.sub.3 H.sub.7                                                                   "     n-C.sub.4 H.sub.9                                                                          " 111-112                            133   "  "      "  "    "                                                                                     ##STR33##  " 125-130                            134   "  "      "  CH.sub.2 C.sub.6 H.sub.5                                                            "     CH.sub.3    " 145-147                            135   "  "      "  n-C.sub.3 H.sub.7                                                                   "     "           " 186-189                            136   "  CH.sub.3                                                                              "  Cl   "     "           " 216-217                            137   "  H      Cl CH.sub.3                                                                            "     "           " 194-196                            138   "  Cl     H  CF.sub.3                                                                            "     C.sub.2 H.sub.5                                                                            " 139-142                            139   "  "      "  "    "     n-C.sub.6 H.sub.13                                                                         "  98-100                            140   "  CH.sub.3                                                                              Cl H    "     CH.sub.3    " 253-255                            141   Cl "      H  "    "     "           " 222-223                            142   H  H      "  CH.sub.2 C.sub.6 H.sub.5                                                            "     i-C.sub.5 H.sub.11                                                                         " 135-136                            143   "  "      "  "    "     n-C.sub.4 H.sub.9                                                                          " 124-125                            144   "  Cl     "  F    "     CH.sub.3    " 217-218                            145   "  NO.sub.2                                                                              "  Cl   "     "           " 190-192                            146   CH.sub.3                                                                          H      H  Cl   CH.sub.3                                                                             CH.sub.3    1 187-188                            147   H  F      "  "    "     "           " 220-221                            148   CF.sub.3                                                                          H      "  OCH.sub.3                                                                           "     "           " 201-202                            149   H  OCH.sub.3                                                                             H  OCH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3    0 178-180                            150   "  "      "  "    "     "           1 231-232                            151   "  H      Cl Cl   "     C.sub.3 H.sub.7                                                                            0 93-95                              152   "  "      "  "    "     "           1 130-132                            153   "  F      F  F    "     CH.sub.3    " 184-186                            154   "  n-C.sub.6 H.sub.13                                                                    H  H    "     "           " 152-154                            155   "  Cl     CF.sub.3                                                                          "    "     "           " 265-267                            156   "  H      F  CF.sub.3                                                                            "     "           " 247-250                            157   "  F      H  CF.sub.3                                                                            "     "           " 202-204                            158   "  H      Cl Cl   "     C.sub.2 H.sub.5                                                                            " 143-146                            159   "  "      "  "    "     sec-C.sub.4 H.sub.9                                                                        0 78-80                              160   "  Cl     NO.sub.2                                                                          HY   "     CH.sub.3    " 281-283                            161   "  "      "  "    "     "           1 253-255                            162   "  H      Cl Cl   "     sec-C.sub.4 H.sub.9                                                                        0 165-168                            163   "                                                                                  ##STR34##                                                                            H  H    "     CH.sub.3    " 208-210                            164   "  "      "  "    "     "           1 210-213                            165   Cl Cl     "  Cl   "     "           0 181-183                            166   "  "      "  "    "     "           1 267-270                            167   H  "      Cl "    "     "           0 --                                 168   "  "      "  "    "     "           1 183-184                            169   Cl "      "  H    "     "           0 264-266                            170   "  "      "  "    "     "           1 --                                 171   "  H      H  NO.sub.2                                                                            "     "           1 202-204                            172   Cl H      H  NO.sub.2                                                                            CH.sub.3                                                                             CH.sub.3    0 197-199                            173   H  CH.sub.3                                                                              "  F    "     "           " 134-135                            174   "  "      "  "    "     "           1 233-235                            175   "  F      "  CH.sub.3                                                                            "     "           0 160-161                            176   "  "      "  "    "     "           1 201-202                            177   "  H      "  OC.sub.6 H.sub.5                                                                    "     "           0 152-153                            178   "  "      "  "    "     "           1 213-214                            179   "  OCF.sub.3                                                                             "  H    "     "           0 167-168                            180   "  "      "  "    "     "           1 248-251                            181   "  Cl     "  CF.sub.3                                                                            "                                                                                     ##STR35##  " 187-188                            182   Cl H      "  Cl   "     "           0 217-218                            183   H  Cl     "  CF.sub.3                                                                            "     "           " 155-157                            184   Cl H      "  Cl   "     "           1 248-250                            185   H  Cl     "  CF.sub.3                                                                             ##STR36##                                                                           CH.sub.3    0 244-245                            186   "  "      "  "                                                                                    ##STR37##                                                                           "           " 191-192                            187   "  "      "  "    "     "           1 156-157                            188   "  H      Cl Cl   CH.sub.3                                                                              ##STR38##  0 225-226                            189   "  Cl     H  CF.sub.3                                                                            C.sub.2 H.sub.5                                                                      CH.sub.3    " 101-102                            190   "  "      "  "    "     "           1 197-198                            191   "  H      "  Br   CH.sub.3                                                                             "           0 167-168                            192   "  "      Cl Cl   C.sub.2 H.sub.5                                                                      "           " 150-151                            193   "  "      "  "    CH.sub.3                                                                             CH.sub.2 CF.sub.3                                                                          " 160-161                            194   "  Cl     H  CF.sub.3                                                                            "     "           " 103-104                            195   "  "      "  "    n-C.sub.3 H.sub.7                                                                    CH.sub.3    " 112-113                            196   "  H      Cl Cl   C.sub.2 H.sub.5                                                                      "           1 204-205                            197   "  Cl     H  CF.sub.3                                                                             ##STR39##                                                                           "           0 129-130                            198   H  Cl     H  CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                    CH.sub.3    1 160-161                            199   "  "      "  "                                                                                    ##STR40##                                                                           "           " 188-189                            200   "  H      "  "    CH.sub.2 C.sub.6 H.sub.5                                                             "           0 102-103                            201   "  COC.sub.6 H.sub.5                                                                     "  NO.sub.2                                                                            CH.sub.3                                                                             "           " 209-210                            202   "  H      "  CF.sub.3                                                                            i-C.sub.3 H.sub.7                                                                    "           " 55-56                              203   "  "      "  "    "     "           1 134-135                            204   "  Cl     "  "    "     "           0 94-95                              205   "  "      "  "    "     "           1 148-149                            206   "  "      "  "    i-C.sub.4 H.sub.9                                                                    "           0 78-79                              207   "  "      "  "    "     "           1 129-130                            208   "  H      F  CH.sub.3                                                                            CH.sub.3                                                                             "           0 116-119                            209   "  "      "  "    "     "           1 182-184                            210   "  "      H  CF.sub.3                                                                            CH.sub.2 SC.sub.6 H.sub.5                                                            "           0 149-150                            211   Cl H      H  CH.sub.3                                                                             ##STR41##                                                                           CH.sub.3    " 100-101                            212   "  "      "  "    "     "           1 208-209                            213   H  "      Cl H    i-C.sub.3 H.sub.7                                                                    "           0 218-220                            214   "  "      "  "    "     "           1 211-213                            __________________________________________________________________________

                  TABLE 2                                                          ______________________________________                                         4-alkoxy or 4-aryloxy-2-quinolinone(Ic)                                         ##STR42##                                                                     Comp.                                                                          No.   R.sub.1                                                                              R.sub.2                                                                              R.sub.3                                                                            R.sub.4                                                                             R.sub.5                                                                             R.sub.9    m.p. (°C.)                   ______________________________________                                         215   H     Cl    H   CF.sub.3                                                                            CH.sub.3                                                                            C.sub.2 H.sub.5                                                                           79-80                               216   "     H     "   "    "    n-C.sub.3 H.sub.7                                                                         --                                  217   "     "     "   "    "                                                                                    ##STR43## 57-58                               218   "     "     "   "    "    i-C.sub.3 H.sub.7                                                                         103-104                             219   "     "     "   "    "    n-C.sub.4 H.sub.9                                                                         31-32                               220   "     "     Cl  Cl   "                                                                                    ##STR44## 192-193                             221   Cl    "     H   "    "    "          165-166                             222   H     Cl    "   CF.sub.3                                                                            "    "          157-158                             ______________________________________                                    

                                      TABLE 3                                      __________________________________________________________________________     4-amino-2-quinolinone(Id)                                                       ##STR45##                                                                     Comp. No.                                                                            R.sub.1                                                                           R.sub.2                                                                               R.sub.3                                                                           R.sub.4                                                                             CH.sub.3                                                                           NAB                      m.p.(°C.)          __________________________________________________________________________     223   H  Cl     H  CF.sub.3                                                                            CH.sub.3                                                                            ##STR46##               149-151                   224   "  "      "  "    "                                                                                   ##STR47##               177-178                   225   "  "      "  "    "                                                                                   ##STR48##               135-136                   226   "  "      "  "    "                                                                                   ##STR49##               218-220                   227   "  "      "  "    "                                                                                   ##STR50##               166-168                   228   "  "      "  "    "                                                                                   ##STR51##               217-218                   229   "  H      "  Cl   C.sub.2 H.sub.5                                                                     ##STR52##               164-166                   230   "  "      "  CH.sub.3                                                                            CH.sub.3                                                                           "                        158-161                   231   "  Cl     "  CF.sub.3                                                                            "                                                                                   ##STR53##               113-115                   232   "  "      "  "    "                                                                                   ##STR54##               195-197                   233   "  "      "  "    "                                                                                   ##STR55##               139-144                   234   "  "      "  "    "                                                                                   ##STR56##               173-174                   235   "  "      "  "    "                                                                                   ##STR57##               153-155                   236   "  "      "  "    "                                                                                   ##STR58##               133-134                   237   "  "      "  "    "                                                                                   ##STR59##               149-151                   238   "  "      "  "    "                                                                                   ##STR60##               113-115                   239   "  "      "  "    "                                                                                   ##STR61##               145-147                   240   "  "      "  "    "                                                                                   ##STR62##               137-140                   241   "  "      "  "    "                                                                                   ##STR63##               188-190                   242   "  "      "  "    "                                                                                   ##STR64##               113-114                   243   H  Cl     H  CF.sub.3                                                                            CH.sub.3                                                                            ##STR65##               131-135                   244   "  "      "  "    "                                                                                   ##STR66##               71-74                     245   "  "      "  "    "                                                                                   ##STR67##               111-113                   246   "  "      "  "    "                                                                                   ##STR68##               168-170                   247   "  "      "  "    "                                                                                   ##STR69##               189-191                   248   "  H      "  F    "                                                                                   ##STR70##               --                        249   "  "      "  "    "                                                                                   ##STR71##               142-145                   250   "  Cl     "  CF.sub.3                                                                            "                                                                                   ##STR72##               66-68                     251   "  "      "  "    "                                                                                   ##STR73##               171-173                   252   "  "      "  "    "                                                                                   ##STR74##               157-159                   253   "  "      "  "    "                                                                                   ##STR75##               163-167                   254   "  H      "  F    "   NHCH.sub.3               146-150                   255   "  "      "  "    "   NHC.sub.2 H.sub.5        --                        256   "  "      "  "    "                                                                                   ##STR76##               151-153                   257   "  Cl     "  CF.sub.3                                                                            "                                                                                   ##STR77##               128-131                   258   "  "      "  "    "                                                                                   ##STR78##               150-152                   259   "  "      "  "    "   NHCH.sub.3               214-216                   260   "  H      "  "    "                                                                                   ##STR79##               196-198                   261   "  "      "  "    "                                                                                   ##STR80##               137-140                   262   "  "      "  "    "                                                                                   ##STR81##               160-161                   263   H  H      H  CF.sub. 3                                                                           CH.sub.3                                                                            ##STR82##               148-153                   264   "  "      "  "    "                                                                                   ##STR83##               124-126                   265   "  "      "  "    "                                                                                   ##STR84##               167-169                   266   "  "      "  "    "   NHCH.sub.3                                         267   "  "      "  "    "                                                                                   ##STR85##               141-143                   268   "  "      "  "    "                                                                                   ##STR86##               131-133                   269   "  "      "  "    "                                                                                   ##STR87##               128-130                   270   "  "      "  "    "                                                                                   ##STR88##               178-180                   271   "  "      "  "    "                                                                                   ##STR89##               159-163                   272   "  Cl     "  "    "                                                                                   ##STR90##               92-93                     273   "  "      "  "    "                                                                                   ##STR91##               89-92                     274   "  "      "  "    "                                                                                   ##STR92##               179-181                   275   "  "      "  "    "                                                                                   ##STR93##               199-202                   276   "  "      "  "    "                                                                                   ##STR94##               71-74                     277   "  "      "  "    "                                                                                   ##STR95##               173-174                   278   NO.sub.2                                                                          H      "  F    "                                                                                   ##STR96##               230-231                   279   H  "      "  CN   "                                                                                   ##STR97##               159-162                   280   "  "      "  CF.sub.3                                                                            "                                                                                   ##STR98##               132-135                   281   "  "      "  "    "                                                                                   ##STR99##               --                        282   "  F      Cl H    "                                                                                   ##STR100##              254-256                   283   H  F      Cl H    CH.sub.3                                                                            ##STR101##              190-192                   284   "  Cl     H  Cl   "                                                                                   ##STR102##              166-167                   285   "  "      "  "    "                                                                                   ##STR103##              168-169                   286   "  "      "  "    "                                                                                   ##STR104##              143-144                   267   "  "      "  "    "                                                                                   ##STR105##              167-168                   288   "  "      "  "    "                                                                                   ##STR106##              119-120                   289   "  "      "  "    "                                                                                   ##STR107##              102-103                   290   NO.sub.2                                                                          H      "  F    "                                                                                   ##STR108##              231-233                   291   H  "      "  CF.sub.3                                                                            "                                                                                   ##STR109##              80-86                     292   "  Cl     "  Cl   "                                                                                   ##STR110##              202-203                   293   "  "      "  "    "                                                                                   ##STR111##              100-101                   294   "  "      "  "    "                                                                                   ##STR112##              130-131                   295   "  "      "  "    "                                                                                   ##STR113##              107-108                   296   "  "      "  "    "                                                                                   ##STR114##              146-148                   297   "  "      "  "    "                                                                                   ##STR115##              158-159                   298   "  "      "  "    "                                                                                   ##STR116##              186-188                   299   "  F      Cl H    "                                                                                   ##STR117##              194- 196                  300   CF.sub.3                                                                          H      H  Cl   "                                                                                   ##STR118##              174-175                   301   "  "      "  "    "                                                                                   ##STR119##              205-207                   302   "  "      "  "    "                                                                                   ##STR120##              208-209                   303   "  "      "  "    "                                                                                   ##STR121##              142-143                   304   H  "      "  CF.sub.3                                                                            "                                                                                   ##STR122##              178-180                   305   "  "      "  "    "                                                                                   ##STR123##              111-113                   306   NO.sub.2                                                                          H      H  Cl   CH.sub.3                                                                            ##STR124##              224-229                   307   "  "      "  "    "                                                                                   ##STR125##              191-200                   308   "  "      "  "    "                                                                                   ##STR126##              217-220                   309   "  "      "  "    "                                                                                   ##STR127##              249-250                   310   H  Cl     "  "    "                                                                                   ##STR128##              193-194                   311   "  "      "  "    "                                                                                   ##STR129##              162-163                   312   "  "      "  "    "                                                                                   ##STR130##              175-176                   313   "  "      "  "    "                                                                                   ##STR131##              142-143                   314   "  F      Cl H    "                                                                                   ##STR132##              259-262                   315   "  H      H  CF.sub.3                                                                            "                                                                                   ##STR133##              190-193                   316   NO.sub.2                                                                          "      "  Cl   "                                                                                   ##STR134##              215-217                   317   "  "      "  "    "                                                                                   ##STR135##              150-153                   318   "  "      "  "    "                                                                                   ##STR136##              216-218                   319   "  "      "  "    "                                                                                   ##STR137##              201-203                   320   H  F      Cl H    "                                                                                   ##STR138##              193-195                   321   NO.sub.2                                                                          H      H  Cl   "                                                                                   ##STR139##              217-219                   322   "  "      "  "    "                                                                                   ##STR140##              200-203                   323   "  "      "  "    "                                                                                   ##STR141##              221-223                   324   "  "      "  "    "                                                                                   ##STR142##              228-230                   325   "  "      "  "    "                                                                                   ##STR143##              232-234                   326   "  "      "  "    "                                                                                   ##STR144##              214-215                   327   H  F      Cl H    "                                                                                   ##STR145##              257-260                   328   H  F      Cl H    CH.sub.3                                                                            ##STR146##              >260                      329   "  H      H  CF.sub.3                                                                            "                                                                                   ##STR147##              113-116                   330   "  "      "  "    "                                                                                   ##STR148##              105-107                   331   "  Cl     "  CH.sub.3                                                                            "                                                                                   ##STR149##              231-233                   332   "  "      "  "    "                                                                                   ##STR150##              121-124                   333   "  "      "  "    "                                                                                   ##STR151##              148-150                   334   "  "      "  "    "                                                                                   ##STR152##              122-126                   335   "  "      "  "    "                                                                                   ##STR153##              118-122                   336   "  "      "  "    "                                                                                   ##STR154##              158-160                   337   "  "      "  "    "                                                                                   ##STR155##              111-112                   338   "  "      "  "    "                                                                                   ##STR156##              205-209                   339   "  "      "  "    "                                                                                   ##STR157##              190-192                   340   "  "      "  "    "                                                                                   ##STR158##              195-197                   341   "  "      "  "    "                                                                                   ##STR159##              181-183                   342   "  H      "  CF.sub.3                                                                            "                                                                                   ##STR160##              135-137                   343   "  "      "  "    "                                                                                   ##STR161##              135-137                   344   "  "      "  "    "                                                                                   ##STR162##              169-171                   345   "  "      "  "    "                                                                                   ##STR163##              164-166                   346   "  "      "  "    "                                                                                   ##STR164##              180-183                   347   "  Cl     "  Cl   "                                                                                   ##STR165##              118-120                   348   H  Cl     H  Cl   CH.sub.3                                                                            ##STR166##              120-121                   349   "  "      "  "    "                                                                                   ##STR167##              94-95                     350   "  "      "  "    "                                                                                   ##STR168##              --                        351   "  F      Cl H    "                                                                                   ##STR169##              234-236                   352   "  NO.sub.2                                                                              H  "    "                                                                                   ##STR170##              >260                      353   "  "      "  "    "                                                                                   ##STR171##              254-256                   354   "  H      "  CF.sub.3                                                                            "                                                                                   ##STR172##              205-208                   355   "  "      "  "    "                                                                                   ##STR173##              181-185                   356   "  "      "  "    "                                                                                   ##STR174##              159-164                   357   "  t-C.sub.4 H.sub.9                                                                     "  H    "                                                                                   ##STR175##              217-219                   358   "  "      "  "    "                                                                                   ##STR176##              182-184                   359   "  "      "  "    "                                                                                   ##STR177##              219-220                   360   "  "      "  "    "                                                                                   ##STR178##              243-245                   361   "  "      "  "    "                                                                                   ##STR179##              185-186                   362   "  "      "  "    "                                                                                   ##STR180##              141-143                   363   "  H      "  CF.sub.3                                                                            "                                                                                   ##STR181##              188-190                   364   "  "      "  "    "                                                                                   ##STR182##              142-143                   365   "  Cl     "  Cl   "                                                                                   ##STR183##              118-120                   366   "  t-C.sub.4 H.sub.9                                                                     "  H    "   NHC.sub.2 H.sub.5        266-267                   367   "  "      "  "    "                                                                                   ##STR184##              233-235                   368   "  Cl     "  CH.sub.3                                                                            "                                                                                   ##STR185##              112-116                   369   H  Cl     H  CH.sub.3                                                                            CH.sub.3                                                                            ##STR186##              168-170                   370   "  "      "  "    "                                                                                   ##STR187##              164-167                   371   "  "      "  "    "                                                                                   ##STR188##              201-203                   372   "  "      "  "    "                                                                                   ##STR189##              186-191                   373   "  "      "  "    "                                                                                   ##STR190##              208-209                   374   "  "      "  "    "                                                                                   ##STR191##              154-155                   375   "  "      "  "    "                                                                                   ##STR192##              178-182                   376   "  t-C.sub.4 H.sub.9                                                                     "  H    "                                                                                   ##STR193##              175-176                   377   "  "      "  "    "                                                                                   ##STR194##              253-254                   378   "  "      "  "    "                                                                                   ##STR195##              231-233                   379   "  Cl     "  CH.sub.3                                                                            "                                                                                   ##STR196##              170-172                   380   "  "      "  "    "                                                                                   ##STR197##              193-196                   381   "  "      "  "    "                                                                                   ##STR198##              193-195                   382   "  "      "  "    "                                                                                   ##STR199##              239-241                   383   "  "      "  "    "                                                                                   ##STR200##              255-257                   384   "  "      "  "    "                                                                                   ##STR201##              219-220                   385   "  "      "  "    "   NHC.sub.2 H.sub.5        202-203                   386   "  H      "  C.sub.2 H.sub.5                                                                     "                                                                                   ##STR202##              168-169                   387   "  "      "  "    "                                                                                   ##STR203##              186-187                   388   "  "      "  "    "                                                                                   ##STR204##              169-171                   389   H  H      H  C.sub.2 H.sub.5                                                                     CH.sub.3                                                                            ##STR205##              188-190                   390   "  "      "  "    "                                                                                   ##STR206##              80-82                     391   "  "      "  "    "                                                                                   ##STR207##              114-115                   392   "  "      "  "    "                                                                                   ##STR208##              163-164                   393   "  "      "  "    "                                                                                   ##STR209##              143-145                   394   "  "      "  "    "                                                                                   ##STR210##              137-139                   395   "  "      "  "    "                                                                                   ##STR211##              181-183                   396   "  "      "  "    "                                                                                   ##STR212##              108-109                   397   "  "      "  "    "                                                                                   ##STR213##              99-100                    398   "  "      "  "    "                                                                                   ##STR214##              148-150                   399   "  "      "  "    "                                                                                   ##STR215##              150-153                   400   "  "      "  "    "                                                                                   ##STR216##              114-116                   401   "  "      "  "    "                                                                                   ##STR217##              180-182                   402   "  "      "  "    "                                                                                   ##STR218##              139-140                   403   "  "      "  "    "                                                                                   ##STR219##              148-150                   404   "  Cl     "  CF.sub.3                                                                            "                                                                                   ##STR220##              127-128                   405   "  "      "  "    "                                                                                   ##STR221##              192-194                   406   "  "      "  "    "                                                                                   ##STR222##              228-231                   407   "  "      "  "    "                                                                                   ##STR223##              171-172                   408   "  "      "  "    "                                                                                   ##STR224##              203-205                   409   "  "      "  "    "                                                                                   ##STR225##              244-246                   410   H  Cl     H  CF.sub.3                                                                            CH.sub.3                                                                            ##STR226##              226-228                   411   "  "      "  "    "                                                                                   ##STR227##              332-335                   412   "  "      "  "    "                                                                                   ##STR228##              173-175                   413   "  "      "  CH.sub.3                                                                            "                                                                                   ##STR229##              216-220                   414   "  "      "  "    "   NHCH.sub.3               250-252                   415   "  "      "  "    "                                                                                   ##STR230##              221-222                   416   "  "      "  "    "                                                                                   ##STR231##              209-211                   417   "  "      "  "    "                                                                                   ##STR232##              210-212                   418   "  "      "  "    "                                                                                   ##STR233##              141-160                   419   "  "      "  "    "                                                                                   ##STR234##              305-308                   420   "  "      "  "    "                                                                                   ##STR235##              195-197                   421   "  "      "  "    "                                                                                   ##STR236##              141-144                   422   "  "      "  "    "                                                                                   ##STR237##              155-156                   423   "  "      "  "    "                                                                                   ##STR238##              194-195                   424   "  "      "  "    "                                                                                   ##STR239##              165-167                   425   "  "      "  "    "                                                                                   ##STR240##              196-198                   426   "  t-C.sub.4 H.sub.9                                                                     "  "    "                                                                                   ##STR241##              231-232                   427   "  "      "  "    "                                                                                   ##STR242##              235-236                   428   "  "      "  "    "                                                                                   ##STR243##              161-163                   429   "  "      "  "    "                                                                                   ##STR244##              187-189                   __________________________________________________________________________

    __________________________________________________________________________     430   H  t-C.sub.4 H.sub.9                                                                     H  H    CH.sub.3                                                                            ##STR245##              172-173                   431   "  "      "  "    "                                                                                   ##STR246##              208-210                   432   "  "      "  "    "                                                                                   ##STR247##              217-218                   433   "  "      "  "    "                                                                                   ##STR248##              253-255                   434   "  "      "  "    "                                                                                   ##STR249##              236-238                   435   "  Cl     "  CF.sub.3                                                                            "                                                                                   ##STR250##              122-124                   436   "  "      "  "    "                                                                                   ##STR251##              167-169                   437   "  "      "  "    "                                                                                   ##STR252##              202-204                   438   "  "      "  "    "                                                                                   ##STR253##              204-206                   439   "  "      "  "    "                                                                                   ##STR254##              184-186                   440   "  "      "  "    "                                                                                   ##STR255##              126-129                   441   "  "      "  "    "                                                                                   ##STR256##              173-174                   442   CF.sub.3                                                                          H      "  Cl   "                                                                                   ##STR257##              206-208                   443   "  "      "  "    "                                                                                   ##STR258##              168-170                   444   "  "      "  "    "                                                                                   ##STR259##              165-167                   445   "  "      "  "    "                                                                                   ##STR260##              184-187                   446   "  "      "  "    "                                                                                   ##STR261##              178-179                   447   "  "      "  "    "                                                                                   ##STR262##              173-175                   448   H  BR     CF.sub.3                                                                          H    "                                                                                   ##STR263##              231-233                   449   "  "      "  "    "                                                                                   ##STR264##              213-215                   450   H  BR     CF.sub.3                                                                          H    CH.sub.3                                                                            ##STR265##              258-259                   451   "  "      "  "    "                                                                                   ##STR266##              261-263                   452   "  "      "  "    "                                                                                   ##STR267##              275-278                   453   "  "      "  "    "                                                                                   ##STR268##              232-234                   454   CF.sub.3                                                                          H      H  Cl   "                                                                                   ##STR269##              189-190                   455   "  "      "  "    "                                                                                   ##STR270##              235-238                   456   "  "      "  "    "                                                                                   ##STR271##              225-226                   457   "  "      "  "    "                                                                                   ##STR272##              186-188                   458   "  "      "  "    "                                                                                   ##STR273##              174-176                   459   "  "      "  "    "                                                                                   ##STR274##              218-219                   460   "  "      "  "    "                                                                                   ##STR275##              231-235                   461   "  "      "  "    "                                                                                   ##STR276##              208-210                   462   H  Cl     CF.sub.3                                                                          H    "                                                                                   ##STR277##              239-240                   463   "  "      "  "    "                                                                                   ##STR278##              223-226                   464   "  "      "  "    "                                                                                   ##STR279##              249-250                   465   "  "      "  "    "                                                                                   ##STR280##              259-260                   466   "  "      "  "    "                                                                                   ##STR281##              217-222                   467   "  "      "  "    "                                                                                   ##STR282##              232-234                   468   "  "      "  "    "                                                                                   ##STR283##              192-194                   469   "  H      "  "    "                                                                                   ##STR284##              233-235                   470   H  H      CF.sub.3                                                                          H    CH.sub.3                                                                            ##STR285##              238-240                   471   "  "      "  "    "                                                                                   ##STR286##              266-268                   472   "  "      "  "    "                                                                                   ##STR287##              234-236                   473   "  "      "  "    "                                                                                   ##STR288##              251-252                   474   "  "      "  "    "                                                                                   ##STR289##              238-239                   475   "  "      Cl Cl   "                                                                                   ##STR290##              110-111                   476   "  "      "  "    "                                                                                   ##STR291##              162-164                   477   "  "      "  "    "                                                                                   ##STR292##              190-198                   478   "  "      "  "    "                                                                                   ##STR293##              133-135                   479   "  "      "  "    "                                                                                   ##STR294##              112-114                   480   "  "      "  "    "                                                                                   ##STR295##              201-203                   481   "  "      "  "    "                                                                                   ##STR296##              173-174                   482   "  "      "  "    "                                                                                   ##STR297##              175-176                   483   "  "      "  "    "                                                                                   ##STR298##              172-173                   484   "  "      "  "    "                                                                                   ##STR299##              150-151                   485   "  "      "  "    "                                                                                   ##STR300##              153-155                   486   "  "      "  "    "                                                                                   ##STR301##              85-86                     487   "  "      "  "    "                                                                                   ##STR302##              197-198                   488   "  "      "  "    "   NHCH.sub.3               213-215                   489   CF.sub.3                                                                          "      H  "    "                                                                                   ##STR303##              177-178                   490   "  "      "  "    "                                                                                   ##STR304##              211-213                   491   "  "      "  "    "                                                                                   ##STR305##              133-135                   492   CF.sub.3                                                                          H      H  Cl   CH.sub.3                                                                            ##STR306##              209-212                   493   "  "      "  "    "                                                                                   ##STR307##              222-224                   494   "  "      "  "    "                                                                                   ##STR308##              160-161                   495   Cl "      "  "    "                                                                                   ##STR309##              179-180                   496   "  "      "  "    "                                                                                   ##STR310##               205                      497   "  "      "  "    "                                                                                   ##STR311##              216-217                   498   "  "      "  "    "                                                                                   ##STR312##              232-234                   499   "  "      "  "    "                                                                                   ##STR313##              175-177                   500   "  "      "  "    "                                                                                   ##STR314##              164-165                   501   "  "      "  "    "                                                                                   ##STR315##              184-185                   502   "  "      "  "    "                                                                                   ##STR316##              176-178                   503   "  "      "  "    "                                                                                   ##STR317##              190-192                   504   "  "      "  "    "                                                                                   ##STR318##              235-237                   505   H  Cl     CF.sub.3                                                                          H    "                                                                                   ##STR319##              239-242                   506   "  "      "  "    "                                                                                   ##STR320##              285-286                   507   "  "      "  "    "                                                                                   ##STR321##              167-173                   508   "  "      "  "    "                                                                                   ##STR322##              192-193                   509   "  "      "  "    "                                                                                   ##STR323##              211-212                   510   "  "      "  "    "                                                                                   ##STR324##              245-247                   511   "  "      "  "    "                                                                                   ##STR325##              235-239                   512   Cl H      H  Cl   "                                                                                   ##STR326##              170-173                   513   "  "      "  "    "                                                                                   ##STR327##              149-150                   514   CF.sub.3                                                                          "      "  "    "                                                                                   ##STR328##              223-226                   515   H  Cl     H  CH.sub.3                                                                            NHCH.sub.3                                                                         266-268                                            516   "  H      "  C.sub.2 H.sub.5                                                                     "   "                        168-170                   517   "  OCH.sub.3                                                                             "  H    "   "                        248-250                   518   CF.sub.3                                                                          H      "  Cl   "   "                        270-274                   519   H  H      "  "    ""  211-213                                            520   "  Cl     CF.sub.3                                                                          H    "   "                        275-277                   521   "  H      "  "    "                                                                                   ##STR329##              277-279                   522   "  CF.sub.3                                                                              H  H    "                                                                                   ##STR330##              235-237                   523   "  "      "  "    "                                                                                   ##STR331##              225-227                   524   "  "      "  "    "                                                                                   ##STR332##              254-257                   525   "  Cl     "  CH.sub.3                                                                            "                                                                                   ##STR333##              197-198                   526   "  "      CF.sub.3                                                                          H    "                                                                                   ##STR334##              111-116                   527   "  "      "  "    "                                                                                   ##STR335##              276-277                   528   Cl H      H  CH.sub.3                                                                            "                                                                                   ##STR336##              164-166                   529   "  "      "  "    "                                                                                   ##STR337##              215-216                   530   "  "      "  "    "                                                                                   ##STR338##              184-185                   531   "  "      "  "    "                                                                                   ##STR339##              207-208                   532   "  "      "  "    "                                                                                   ##STR340##              182-185                   533   CH.sub.3                                                                          H      CH.sub.3                                                                          H    "                                                                                   ##STR341##              140-142                   534   "  "      "  "    "                                                                                   ##STR342##              145-146                   535   "  "      "  "    "                                                                                   ##STR343##              213-214                   536   "  "      "  "    "                                                                                   ##STR344##              220-222                   537   "  "      "  "    "                                                                                   ##STR345##              117-120                   538   CH.sub.3                                                                          H      CH.sub.3                                                                          H    CH.sub.3                                                                            ##STR346##              203-205                   539   "  "      "  "    "                                                                                   ##STR347##              182-184                   540   H  CF.sub.3                                                                              H  "    "                                                                                   ##STR348##              205-210                   541   "  "      "  "    "                                                                                   ##STR349##              137-138                   542   "  "      "  "    "                                                                                   ##STR350##              124-126                   543   "  H      "  I-C.sub.3 H.sub.7                                                                   "                                                                                   ##STR351##              126-128                   544   "  "      "  "    "                                                                                   ##STR352##              154-155                   545   "  "      "  "    "                                                                                   ##STR353##              107-108                   546   "  "      "  "    "                                                                                   ##STR354##              114-115                   547   NO.sub.2                                                                          "      "  Cl   "                                                                                   ##STR355##              202-203                   548   "  "      "  "    "                                                                                   ##STR356##              258-259                   549   "  "      "  "    "                                                                                   ##STR357##              251- 254                  550   "  "      "  "    "                                                                                   ##STR358##              246-248                   551   "  "      "  "    "                                                                                   ##STR359##              242-245                   552   "  "      "  "    "                                                                                   ##STR360##              206-208                   553   "  "      "  "    "                                                                                   ##STR361##              242-244                   554   Cl "      Cl H    "                                                                                   ##STR362##              192-195                   555   "  "      "  "    "                                                                                   ##STR363##              124-125                   556   "  "      "  "    "                                                                                   ##STR364##              128-130                   557   "  "      H  CH.sub.3                                                                            "                                                                                   ##STR365##              213-214                   558   NO.sub.2                                                                          "      "  OCH.sub.3                                                                           "                                                                                   ##STR366##              162-165                   559   "  "      "  "    "                                                                                   ##STR367##              175-176                   __________________________________________________________________________

    __________________________________________________________________________     560   NO.sub.2                                                                          H      H  OCH.sub.3                                                                           CH.sub.3                                                                            ##STR368##              135-138                   561   "  "      "  "    "                                                                                   ##STR369##              178-179                   562   "  "      "  Cl   "                                                                                   ##STR370##              219-220                   563   "  "      "  "    "                                                                                   ##STR371##              266-269                   564   H  "      "  C.sub.6 H.sub.5                                                                     "                                                                                   ##STR372##              142-144                   565   "  "      "  "    "                                                                                   ##STR373##              134-136                   566   "  "      "  "    "                                                                                   ##STR374##              168-169                   567   "  "      "  "    "                                                                                   ##STR375##              198-200                   568   "  "      "  "    "                                                                                   ##STR376##              156-158                   569   "  "      "  "    "   NHCH.sub.3               196-198                   570   "  "      "  "    "                                                                                   ##STR377##              178-180                   571   "  "      "  "    "                                                                                   ##STR378##              182-183                   572   "  "      "  "    "                                                                                   ##STR379##              200-202                   573   "  "      "  "    "                                                                                   ##STR380##              127-133                   574   "  "      "  "    "                                                                                   ##STR381##              193-196                   575   "  "      "  "    "                                                                                   ##STR382##              170-171                   576   "  CH.sub.3                                                                              "  CH.sub. 3                                                                           "                                                                                   ##STR383##              185-186                   577   "  "      "  "    "                                                                                   ##STR384##              108-111                   578   "  "      "  "    "                                                                                   ##STR385##              128-130                   579   "  "      "  "    "                                                                                   ##STR386##              182-183                   580   "  "      "  "    "                                                                                   ##STR387##              85-87                     581   "  "      "  "    "                                                                                   ##STR388##              163-164                   582   H  CH.sub.3                                                                              H  CH.sub.3                                                                            CH.sub.3                                                                            ##STR389##              150-151                   583   "  Cl     "  CF.sub.3                                                                            "                                                                                   ##STR390##              166-174                   584   H  "      "  "    "                                                                                   ##STR391##              164-167                   585   "  "      "  "    "                                                                                   ##STR392##              157-161                   586   "  "      "  "    "                                                                                   ##STR393##              158-160                   587   "  H      "  CH.sub.2 C.sub.6 H.sub.5                                                            "                                                                                   ##STR394##              132-134                   588   "  "      "  "    "                                                                                   ##STR395##              97-98                     589   "  "      "  "    "                                                                                   ##STR396##               98-100                   590   "  "      "  "    "                                                                                   ##STR397##              146-147                   591   "  "      "  "    "                                                                                   ##STR398##              131-132                   592   "  "      "  "    "                                                                                   ##STR399##              138-140                   593   "  "      "  "    "                                                                                   ##STR400##              119-120                   594   "  "      "  "    "                                                                                   ##STR401##              153-154                   595   "  CH.sub.3                                                                              "  CH.sub.3                                                                            "                                                                                   ##STR402##              222-223                   596   "  "      "  "    "                                                                                   ##STR403##              237-239                   597   "  "      "  "    "                                                                                   ##STR404##              223-226                   598   Cl H      Cl H    "                                                                                   ##STR405##              205-207                   599   NO.sub.2                                                                          "      H  OCH.sub.3                                                                           "                                                                                   ##STR406##              210-213                   600   "  "      "  "    "                                                                                   ##STR407##              200-201                   601   "  "      "  "    "                                                                                   ##STR408##              133-134                   602   H  Cl     H  CF.sub.3                                                                            CH.sub.3                                                                            ##STR409##              216-217                   603   "  H      "  n-C.sub.3 H.sub.7                                                                   "                                                                                   ##STR410##              168-170                   604   H  "      "  "    "                                                                                   ##STR411##              174-176                   605   "  "      "  "    "                                                                                   ##STR412##              127-129                   606   "  "      "  "    "                                                                                   ##STR413##              134-136                   607   "  "      "  "    "                                                                                   ##STR414##              106-108                   608   "  "      "  "    "                                                                                   ##STR415##              104-105                   609   "  CH.sub.3                                                                              "  Cl   "                                                                                   ##STR416##              173-175                   610   "  "      "  "    "                                                                                   ##STR417##              103-105                   611   "  "      "  "    "                                                                                   ##STR418##              149-150                   612   "  "      "  "    "                                                                                   ##STR419##              248-251                   613   "  "      "  "    "                                                                                   ##STR420##              147-150                   614   "  "      "  "    "                                                                                   ##STR421##              161-162                   615   "  "      "  "    "                                                                                   ##STR422##              231-233                   616   "  "      "  "    "                                                                                   ##STR423##              128-130                   617   "  "      "  "    "                                                                                   ##STR424##              135-136                   618   "  "      "  "    "                                                                                   ##STR425##              171-172                   619   "  "      "  "    "                                                                                   ##STR426##              236-238                   620   "  Cl     "  CF.sub.3                                                                            "                                                                                   ##STR427##              214-217                   621   "  "      "  "    "                                                                                   ##STR428##              228-231                   622   "  "      "  "    "                                                                                   ##STR429##              201-202                   623   Cl H      Cl H    CH.sub.3                                                                            ##STR430##              187-188                   624   H  CH.sub.3                                                                              Cl "    "                                                                                   ##STR431##              252-255                   625   "  "      "  "    "                                                                                   ##STR432##              228-231                   626   "  "      "  "    "                                                                                   ##STR433##              255-258                   627   "  "      "  "    "                                                                                   ##STR434##              248-251                   628   "  "      "  "    "                                                                                   ##STR435##              263-265                   629   "  "      "  "    "                                                                                   ##STR436##              231-234                   630   "  "      "  "    "                                                                                   ##STR437##              257-258                   631   "  "      "  "    "                                                                                   ##STR438##              295-296                   632   Cl CH.sub.3                                                                              H  "    "                                                                                   ##STR439##              198-199                   633   "  "      "  "    "                                                                                   ##STR440##              217-218                   634   "  "      "  "    "                                                                                   ##STR441##              209-210                   635   "  "      "  "    "                                                                                   ##STR442##              189-190                   636   "  "      "  "    "                                                                                   ##STR443##              198-199                   637   "  "      "  "    "                                                                                   ##STR444##              219-220                   638   "  "      "  "    "                                                                                   ##STR445##              201-202                   639   "  "      "  "    "                                                                                   ##STR446##              224-225                   640   H  Cl     "  F    "                                                                                   ##STR447##              168-170                   641   "  "      "  "    "                                                                                   ##STR448##              148-150                   642   "  "      "  "    "                                                                                   ##STR449##              244-247                   643   "  "      "  "    "                                                                                   ##STR450##              138-140                   644   "  "      "  "    "                                                                                   ##STR451##              235-240                   645   "  "      "  "    "                                                                                   ##STR452##              169-170                   646   H  Cl     H  F    CH.sub.3                                                                            ##STR453##              198-200                   647   "  "      "  "    "                                                                                   ##STR454##              151-153                   648   "  "      "  "    "                                                                                   ##STR455##              150-157                   649   CH.sub.3                                                                          H      "  Cl   "                                                                                   ##STR456##              113-115                   650   "  "      "  "    "                                                                                   ##STR457##               131                      651   "  "      "  "    "                                                                                   ##STR458##              178-181                   652   "  "      "  "    "                                                                                   ##STR459##              187-189                   653   "  "      "  "    "                                                                                   ##STR460##              105-107                   654   "  "      "  "    "                                                                                   ##STR461##              133-134                   655   "  "      "  "    "                                                                                   ##STR462##              174-176                   656   "  "      "  "    "                                                                                   ##STR463##              162-163                   657   "  "      "  "    "                                                                                   ##STR464##              121-122                   658   "  "      "  "    "                                                                                   ##STR465##              137-138                   659   "  "      "  "    "                                                                                   ##STR466##               142                      660   "  "      "  "    "                                                                                   ##STR467##              98-99                     661   H  F      "  Cl   "                                                                                   ##STR468##              192-194                   662   "  "      "  "    "                                                                                   ##STR469##              164-165                   663   "  "      "  "    "                                                                                   ##STR470##              211-215                   664   "  "      "  "    "                                                                                   ##STR471##              194-197                   665   "  "      "  "    "                                                                                   ##STR472##              211-213                   666   "  "      "  "    "                                                                                   ##STR473##              123-125                   667   "  "      "  "    "                                                                                   ##STR474##              210-211                   668   H  F      H  Cl   CH.sub.3                                                                            ##STR475##              140-145                   669   "  "      "  "    "                                                                                   ##STR476##              126-127                   670   "  "      "  "    "                                                                                   ##STR477##              194-197                   671   "  "      "  "    "                                                                                   ##STR478##              205-206                   672   "  "      "  "    "                                                                                   ##STR479##              204-205                   673   "  "      "  "    "                                                                                   ##STR480##              164-165                   674   "  "      Cl H    "                                                                                   ##STR481##              270-280                   675   "  "      "  "    "                                                                                   ##STR482##              288-290                   676   "  "      "  "    "                                                                                   ##STR483##              >260                      677   "  "      "  "    "                                                                                   ##STR484##              265-270                   678   "  "      "  "    "                                                                                   ##STR485##              >300                      679   "  "      "  "    "                                                                                   ##STR486##              275-278                   680   "  "      "  "    "                                                                                   ##STR487##              297-300                   681   "  "      "  "    "                                                                                   ##STR488##              >300                      682   CF.sub.3                                                                          H      H  OCH.sub.3                                                                           "                                                                                   ##STR489##              232-233                   683   "  "      "  "    "                                                                                   ##STR490##              204-206                   684   "  "      "  "    "                                                                                   ##STR491##              231-232                   685   "  "      "  "    "                                                                                   ##STR492##              189-190                   686   "  "      "  "    "                                                                                   ##STR493##              232-234                   687   H  Cl     H  CF.sub.3                                                                            CH.sub.3                                                                            ##STR494##              204-206                   688   "  "      "  "    "                                                                                   ##STR495##              194-195                   689   "  "      "  "    "                                                                                   ##STR496##              143-144                   690   "  "      "  "    "                                                                                   ##STR497##              166-168                   691   "  OCH.sub.3                                                                             "  OCH.sub.3                                                                           "                                                                                   ##STR498##              177-178                   692   "  "      "  "    "                                                                                   ##STR499##              178-180                   693   "  "      "  "    "                                                                                   ##STR500##              226-228                   694   "  "      "  "    "                                                                                   ##STR501##              156-157                   695   "  "      "  "    "                                                                                   ##STR502##              --                        696   "  "      "  "    "                                                                                   ##STR503##              233-234                   697   "  "      "  "    "                                                                                   ##STR504##              140-141                   698   "  Cl     NO.sub.2                                                                          H    "   "                        235-237                   699   "  H      H  F    "                                                                                   ##STR505##              116-118                   700   "  "      "  "    "                                                                                   ##STR506##              121-123                   701   "  "      "  "    "                                                                                   ##STR507##               98-100                   702   "                                                                                  ##STR508##                                                                           "  H    "                                                                                   ##STR509##              79-80                     703   H                                                                                  ##STR510##                                                                           H  H    CH.sub.3                                                                            ##STR511##              250-252                   704   "  "      "  "    "                                                                                   ##STR512##              252-254                   705   Cl Cl     "  Cl   "                                                                                   ##STR513##              140-142                   706   "  "      "  "    "                                                                                   ##STR514##              231-233                   707   "  "      "  "    "                                                                                   ##STR515##              237-239                   708   "  "      "  "    "                                                                                   ##STR516##              126-128                   709   "  "      "  "    "                                                                                   ##STR517##              199-200                   710   "  "      "  "    "                                                                                   ##STR518##              144-145                   711   "  "      "  "    "                                                                                   ##STR519##              198-200                   712   "  "      "  "    "                                                                                   ##STR520##              148-150                   713   "  "      "  "    "                                                                                   ##STR521##              251-253                   714   "  "      "  "    "                                                                                   ##STR522##              205-207                   715   "  "      "  "    "                                                                                   ##STR523##              261-263                   716   "  "      "  "    "                                                                                   ##STR524##              218-219                   717   H  "      H  H    C.sub.6 H.sub.5                                                                     ##STR525##              285-286                   718   "  NO.sub.2                                                                              "  Cl   CH.sub.3                                                                            ##STR526##              155-157                   719   "  "      "  "    "                                                                                   ##STR527##              210-212                   720   "  "      "  "    "                                                                                   ##STR528##              88-90                     721   "  "      "  "    "                                                                                   ##STR529##              166-168                   722   "  "      "  "    "                                                                                   ##STR530##              208-210                   723   H  H      H  H    C.sub.6 H.sub.5                                                                     ##STR531##              293-294                   724   "  "      "  "    "                                                                                   ##STR532##              257-258                   725   "  "      "  "    "                                                                                   ##STR533##              295-296                   726   "  "      "  "    "                                                                                   ##STR534##              >300                      727   "  "      "  "    "                                                                                   ##STR535##              297-298                   728   "  "      "  "    "                                                                                   ##STR536##              238-240                   729   "  NO.sub.2                                                                              "  Cl   CH.sub.3                                                                            ##STR537##              219-220                   730   "  "      "  "    "                                                                                   ##STR538##              168-170                   731   "  H      "  H    C.sub.6 H.sub.5                                                                     ##STR539##              293-294                   732   "  "      "  "    "                                                                                   ##STR540##              281-282                   733   "  "      "  "    "                                                                                   ##STR541##              210-212                   734   "  "      "  "    "                                                        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>260                      741   "  "      "  "    "                                                                                   ##STR549##              166-168                   742   "  "      "  "    "                                                                                   ##STR550##              220-222                   743   Cl Cl     Cl H    CH.sub.3                                                                            ##STR551##              >260                      744   "  "      "  "    "                                                                                   ##STR552##              234-236                   745   "  "      "  "    "                                                                                   ##STR553##              250(dec)                  746   "  "      "  "    "                                                                                   ##STR554##              154-156                   747   "  "      "  "    "  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753   "  "      "  "    "                                                                                   ##STR561##              123-125                   754   "  "      "  "    "                                                                                   ##STR562##              260-261                   755   "  "      "  "    "                                                                                   ##STR563##              220-222                   756   "  "      "  "    "                                                                                   ##STR564##              127-129                   757   "  "      "  "    "                                                                                   ##STR565##               97-100                   758   "  "      "  "    "                                                                                   ##STR566##              115-117                   759   "  "      "  "    "                            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    __________________________________________________________________________     766   H  F      H  CH.sub.3                                                                            CH.sub.3                                                                            ##STR574##              209-210                   767   "  "      "  "    "                                                                                   ##STR575##              147-148                   768   "  "      "  "    "                                                                                   ##STR576##              154-155                   769   "  H      "  OC.sub.6 H.sub.5                                                                    "                                                                                   ##STR577##              163-165                   770   "  "      "  "    "                                                                                   ##STR578##          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 "                                                                                   ##STR585##              243-245                   778   NO.sub.2                                                                          "      "  Cl   "                                                                                   ##STR586##              205-207                   779   H  Cl     "  CF.sub.3                                                                            C.sub.6 H.sub.5                                                                     ##STR587##              164-165                   780   "  "      "  "    "                                                                                   ##STR588##              194-195                   781   "  "      "  "    CH.sub.3                                                                            ##STR589##              236-240                   782   NO.sub.2                                                                          H      "  Cl   "   "                        250-260                   783   "  "      "  "    "                                                                                   ##STR590##              200-202                   784   H  Cl     "  CF.sub.3                                                                            C.sub.6 H.sub.5                                                                     ##STR591##              132-133                   785   "  "      "  "    "                                                                                   ##STR592##              154-155                   786   "  "      "  "    "                                                                                   ##STR593##              222-223                   787   NO.sub.2                                                                          H      "  Cl   CH.sub.3                                                                            ##STR594##              230-233                   788   H  Cl     H  CF.sub.3                                                                            CH.sub.3                                                                            ##STR595##              169-170                   789   "  H      "  H    "                                                                                   ##STR596##              268-270                   790   "  "      Cl Cl   "                                                                                   ##STR597##              213-215                   791   "  "      H  CF.sub.3                                                                            "                                                                                   ##STR598##              225-227                   792   "  "      Cl Cl   "                                                                                   ##STR599##              181-183                   793   "  "      "  "    "                                                                                   ##STR600##              224-225                   794   "  "      "  "    "                                                                                   ##STR601##              192-193                   795   "  "      "  "    "                                                                                   ##STR602##              234-235                   796   "  "      "  "    "                                                                                   ##STR603##              224-225                   797   "  "      "  "    "                                                                                   ##STR604##              205-206                   798   "  "      "  "    "                                                                                   ##STR605##              200-201                   799   "  "      "  "    "                                                    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"                                                                                   ##STR618##              240-241                   812   "  "      "  "    "                                                                                   ##STR619##              212-213                   813   "  H      Cl Cl   "   "                        215-217                   814   Cl "      H  "    "                                                                                   ##STR620##              234-235                   815   "  "      "  "    "                                                                                   ##STR621##              224-225                   816   "  "      "  "    "                                                                                   ##STR622##              208-209                   817   "         "  "    "                                                                                   ##STR623##              210-211                   818   "  "      "  "    "                                                                                   ##STR624##              205-206                   819   "  "      "  "    "                                                                                   ##STR625##              240-241                   820   "  "      "  "    "                                                                                   ##STR626##              263-265                   821   "  "      "  "    "                                                                                   ##STR627##              160-162                   822   "  "      "  "    "                                                                                   ##STR628##              210-211                   823   "  "      "  "    "                                                                                   ##STR629##              160-162                   824   "  "      "  "    "                          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"                                                                                   ##STR636##              225-227                   831   "  "      "  "    "                                                                                   ##STR637##              228-229                   832   "  "      "  "    "                                                                                   ##STR638##              242-243                   833   "  "      "  "    "                                                                                   ##STR639##              221-222                   834   "  "      "  "    "                                                                                   ##STR640##              >260                      835   "  "      "  "    "                                                                                   ##STR641##              268-269                   836   "  Cl     "  CF.sub.3                                                  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872   "  "      "  "    "                                                                                   ##STR678##              169-170                   873   "  "      "  "    "                                                                                   ##STR679##              202-203                   874   "  "      "  "    "                                                                                   ##STR680##              158-159                   875   "  "      "  "    "                                                                                   ##STR681##              190-191                   876   "  "      "  "    "                                                                                   ##STR682##              233-234                   877   "  "      "  "    "                                                                                   ##STR683##              168-169                   878   H  H      H  CF.sub.3                          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217-218                   896   "  "      "  "    "                                                                                   ##STR702##              198-199                   897   "  "      "  "    "                                                                                   ##STR703##              215-218                   898   "  "      "  "    "                                                                                   ##STR704##              193-195                   899   "  "      "  "    "                                                                                   ##STR705##              282-285                   900   H  H      "  i-C.sub.3 H.sub.7                                                                   "                                                                                   ##STR706##              186-189                   901   "  "      "  CH.sub.2 C.sub.6 H.sub.5                                                            "  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228-230                   913   H  "      Cl "    "                                                                                   ##STR719##              224-225                   914   "  "      "  "    "                                                                                   ##STR720##              216-217                   915   "  "      "  "    "                                                                                   ##STR721##              222-223                   916   "  "      "  "    "                                                                                   ##STR722##              204-205                   917   "  "      "  "    "                                                                                   ##STR723##              262-263                   918   "  "      "  "    "                                                                                   ##STR724##              271-274                   919   "  "      "  "    "  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n-C.sub.3 H.sub.7                                                                  "                        159-160                   938   "  "      "  "    "                                                                                   ##STR740##              165-167                   939   "  "      "  "    "                                                                                   ##STR741##              --                        940   "  "      "  "    CH.sub.3                                                                            ##STR742##              >260                      941   "  H      "  "    "                                                                                   ##STR743##              >260                      942   "  "      "  "    i-C.sub.3 H.sub.7                                                                   ##STR744##              103-104                   943   "  "      "  "    "                                                    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                                                    CH.sub.3                                                                           "                        211-213                   951   "  "      "  "    "                                                                                   ##STR751##              208-210                   952   "  "      "  "    "                                                                                   ##STR752##              237-238                   953   Cl "      H  "                                                                                        ##STR753##              --                        __________________________________________________________________________

EXAMPLE 1 3-Acetyl-4-methylthio-2-quinolinone(1)

N-Phenyl-α-(bismethylthioylidene)acetoacetamide(28.1 g, 0.1 mol) was heated and refluxed for 2hr in solvent of dichlorobenzene(300 ml) untill the evolution of methylmercaptane ceased.

The reaction progress was determined by chromatography. When the reaction was completed, the reaction mixture was cooled, and then the precipitate was filtered to give the desired product(19.1 g, yield: 82 % ).

¹ H NMR (DMSO-d₆): δ10.7(s, 1H),8.2˜7.15(m,4H),2.65(s,3H),2.53(s,3H).

EXAMPLE 2 3-Acetyl-7-methoxy-4-methylthio-2-quinolinone (2)

N-(m-Anisyl)-α-(bismethylthioylidene)acetoacetamide(3.1 g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product(2.1g, yield: 82%).

¹ H NMR(CDCl₃): δ10.49(s, 1H), 8.18˜6.68(s, 3H), 3.8(s, 3H), 2.64(s, 3H), 2.53(s, 3H).

EXAMPLE 3 3-Acetyl-8-chloro-4-methylthio-2-quinolinone (3)

N-(2-Chlorophenyl)-α-(bismethylthioylidene)acetoacetamide (3.2g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.2g, yield: 86%).

¹ H NMR (DMSO-d₆ ): δ8.2˜7.25(m, 3H), 4.5˜3.0(brs), 2.67(s, 3H), 2.59(s, 3H).

EXAMPLE 4 3-Acetyl-5,8-dichloro-4-methylthio-2-quinolinone (4)

N-(2,5-Dichlorophenyl)-α-(bismethylthioylidene)acetoacetamide (3.5g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.0g, yield:68%).

¹ H NMR(DMSO-d₆ +CDCl₃): δ7.7 (d, J=9.0, 1H),7.27(d, J=9.0, 1H), 2.64(s,3H), 2.52(s,3H).

EXAMPLE 5 3-Acetyl-6-methoxy-4-methylthio-2-quinolinone (5)

N-(p-Anisyl)-α-(bismethylthioylidene)acetoacetamide (3.1 g, 0.01 mol) was used, but the reaction was camm out as the above process of example 1 to obtain the desired product (1.9g, yield: 74%).

¹ H NMR(DMSO-d₆): δ10.68(s,1H),7.93˜6.95(m,3H),3.83(s,3H), 2.63(s,3H),2.59(s,3H).

EXAMPLE 6 3-Acetyl-6-fluoro-4-methylthio-2-quinolinone (7)

N-(4-Fluorophenyl)-α-(bismethylthioylidene)acetoacetamide (3.0g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.3g, yield: 95%).

¹ H NMR(DMSO-d₆ +CDCl3): δ8.1˜7.2(m,3H),2.62(s,3H), 2.55(s, 3H). EXAMPLE 7

3-Acetyl-8-fluoro-4-methylthio-2-quinolinone (8)

N-(2-Fluorophenyl)-α-(bismeth ylthioylidene)butyrylacetami de (3.0g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.0g, yield: 85%).

¹ H NMR(DMSO-d₆ +CDCl₃): δ6.13˜7.1(m,3H),2.65(s,3H),2.57(s,3H).

EXAMPLE 8 3-Butyryl-8-chloro-4-methylthio-2-quinolinone (9)

N-(2-Chlorophenyl)-α-(bismethyl thioylidene)butyrylacetamide (3.4g, 0.01 mol) was used, but the reaction was carded out as the above process of example 1 to obtain the desired product (2.5g, yield: 895).

¹ H NMR(CDCl₃): δ8.7(s,1H), 8.52˜8.05(m,1H),7.47˜6.75(m,3H), 2.760, (t,J=7.0, 2H),2.45(s,6H), 1.72(m,2H), 2.45(s,6H), 1.72(m,2H), 0.95(t,J=7.0, 3H).

EXAMPLE 9 3-Acetyl-8-methyl-8-methylthio-2-quinolinone (11)

N-(o-Tolyl)-α-(bismethyl thioylidene)acetoacetamide (3.0g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.1g, yield: 88%).

¹ H NMR(DMSO-d₆): δ15.6(s,1H), 8.06˜7.3(m,3H),2.93(s,3H), 2.69(s, 3H), 2.65(s,3H).

EXAMPLE 10 3-Benzoyl-8-chloro-4-methylthio-2-quinolinone (12)

N-(2-Chlorophenyl)-α-(bismethylthioylidene) benzoylacetamide (3.8g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.6g, yield : 81%).

¹ H NMR(DMSO-d₆, CDCl₃): δ8.3˜7.2(m,8H),2.65(s,3H).

EXAMPLE 11 3-Acetyl-6-chloro-8-trifluoroethy14-methylthio-2-quinolinone (13)

N-(4-Chloro-2-trifluoromethylphenyl)-α-(bismethylthioylidene) acetoacetamide (3.8 g, 0.01 mol) was used, but the reaction was carded out as the above process of example 1 to obtain the desired product (2.3g, yield: 71%).

¹ H NMR(CDCl₃ +DMSO-d₆ ): δ8.3(s,1H), 8.12(s,3H), 2.67(s,3H).

EXAMPLE 12 3-Acetyl-8-methoxycarbonyl-4-methylthio-2-quinolinone (16)

N -(2-Methoxycarbonylphenyl)- α-(bismethylthioylidene)acetoacetamide (3.4g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.8g, yield: 99%).

¹ H NMR(DMSO-d₆ +CDCl₃): δ2.6(s,3H), 3.27(s,3H), 4.03(s,3H), 7.4˜8.6(m,3H).

EXAMPLE 13 3-Acetyl-6-nitro-4-methylthio-2-quinolinone (20)

N-(4-Nitrophenyl)-α-(bismethylthioylidene)acetoacetamide (3.3g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.1 g, yield: 80% ).

¹ H NMR(DMSO-d₆ +CDCl₃): δ2.57(s,3H), 2.66(s,3H),8.0˜8.9(m,4H).

EXAMPLE 14 3-Acetyl-6-chloro-7-nitro-4-methylthio-2-quinolinone (21)

N-(3-Nitro-4-chlorophenyl)-α-(bismethyl thioylidene)acetoacemmide (3.6g, 0.01 mol) was used, but the reaction was carded out as the above process of example to obtain the desired product (1.8g, yield: 61%).

¹ H NMR(DMSO-d₆ +CDCl₃): δ2.43(s,3H), 2.7(s,3H), 7.73˜8.13(m,2H), 11.4(s,1H).

EXAMPLE 15 3-Acetyl-8-cyano-4-methylthio-2-quinolinone(22)

N-(2-Cyanophenyl)-α-(bismethylthioylidene)acetoacetamide (3.1g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (1 .8g, yield: 73%).

¹ H NMR(DMSO-d₆ +CDCl₃): δ2.13(s,3H), 2.7(s,3H), 7.6˜8.7(m,3H).

EXAMPLE 16 3-Acetyl-6-chloro-8-trifluoromethyl-4-(t-butylbenzylthio)-2-quinolinone (23)

N-(4-Chloro-2-trifluo romet hylph enyl) -α-[bis-(t-butylbenzylthio)ylidene]acetoacetamide (6.3g, 0.01 mol) was used, but the reaction was carded out as the above process of example 1 to obtain the desired product (2.5g, yield: 54%).

¹ H NMR(DMSO-d₆ +CDCl₃): δ1.27(s,9H), 2.73(s,3H), 4.6(s,2H), 7.35(s,4H), 7.95(d,1H), 8.52(d,1H).

EXAMPLE 17 3-Acetyl-6-t-butyl-4-methylthio-2-quinolinone (24)

N-(4-t-Butylphenyl)-α-(bismethylthioylidene)acetoacetamide (3.4g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.3g, yield: 84%).

¹ H NMR(DMSO-d₆ +CDCl₃): δ1.37(s,9H), 2.6(s,3H), 2.63(s,3H), 7.73(d,2H), 8.23(s,1H), 10.83(s,1H).

EXAMPLE 18 3-Acetyl-5,6,7,8-tetrachloro-4-methylthio-2-quinolinone (27)

N-(2,3,4,5-Tetrachlorophenyl)-α-(bismethylthioylidene)acetoacetamide (3.5g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.6g, yield: 74%).

¹ H NMR(DMSO-d₆ +CDCl₃): δ2.43(s,3H), 2.66(s,3H), 7.96(s,1H).

EXAMPLE 19 3-Acetyl-8-trifluommethyl-4-methylthio-2-quinolinone (29)

N-(2-Tfifiuoromethylphenyl)-α-(bismethylthioylidene)acetoacetamide (3.5 g, 0.01mol) was used, but the reaction was carried out as the above process of example to obtain the desired product (1 .9g, yield: 65%).

¹ H NMR(DMSO-d₆ +CDCl₃): δ2.6(s,3H), 2.7(s,3H), 8.06(m,1H),8.63(m,1H).

EXAMPLE 20 3-Acetyl-8-fluoro-8-trifluoromethyl-4-methylthio-2-quinolinone (33)

N-(4-Fluoro-2-trifluoromethylphenyl)-α-(bismethylthioylidene)acetoacet amide (3.7g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.5g, yield: 83%).

¹ H NMR(CDCl₃): δ2.7(s,3H), 2.97(s,3H), 7.73˜8.16(m,1H), 15.63(s,1H).

EXAMPLE 21 3-Acetyl-7-fluoro-8-trifluoromethyl-4-methylthio-2-quinolinone (34)

N-(2 -Trifluoromethyl-3 -fluorophenyl)-α- (bismethylthioylidene)acetoacet amide (3.7g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.2g, yield: 73%).

¹ H NMR(CDCl₃): δ2.72(s,3H), 2.93(s,3H), 7.1˜7.68(m,1H), 7.83˜8.1(m,2H).

EXAMPLE 22 3-Acetyl-6-bromo-8-trifluoromethyl-4-methylthio-2-quinolinone (35)

N-4-Bromo-8-trifluoromethyl-α-(bismethylthioylidene)acetoacetarnide (4.3g, 0.01 mol) was used, but the reaction was carried out as the above process of example to obtain the desired product (2.5g, yield: 67%).

¹ H NMR(CDCl₃): δ2.7(s,3H), 2.93(s,3H), 8.1(s,1H), 8.53(s,1H), 15.6(s,1H).

EXAMPLE 23 3-Acetyl-6-chloro-7-trifluoromethyl-4-methylthio-2-quinolinone (36)

N-(3-Trifluoromethyl)-α-(bismeth ylthioylidene)acetoacetamide (3.8g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (1 .7g, yield: 52%).

¹ H NMR(CDCl₃): δ2.7(s,3H), 2.92(s,3H), 8.1˜8.3(m,2H), 15.57(s,1H).

EXAMPLE 24 3-Acetyl-6-hexyl-4-methylthio-2-quinolinone (37)

N-4-Hexylphenyl)-α-(bismethylthioylidene)acetoacetamide (3.7 g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.5g, yield: 82%).

¹ H NMR(CDCl₃): δ0.78˜0.97(m,3H), 1.16˜1.8(m,10H), 2.67(s,3H), 2.83(s,3H), 7.57˜8.07(m,3H).

EXAMPLE 25 3-Acetyl-6,7,8-trifluoro-4-methylthio-2-quinolinone (38)

N-(2,3,4-Trifluorophenyl)-α-(bismethylthi oylidene)acetoacetamide (3.4g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (1.8g, yield: 67%).

¹ H NMR(CDCl₃): δ2.73(s,3H), 2.97(s,3H), 7.6˜7.93(m,1H), 15.73(s,1H).

EXAMPLE 26 3-Acetyl-6-chloro-8-trifluoromethyl-4-(2,4-dichlorobenzylthio)-2-quinolinone (39)

N-(4-Chloro- 2-trifluoromethylphenyl)-α-[bis(2,4-dichlorobenzylthio) ylidene]-acetoacetamide (6.0g, 0.01 mol) was used, but the reaction was carried out as the above process of example 1 to obtain the desired product (2.4g, yield: 51%).

¹ H NMR(CDCl₃): δ15.68(s,1H), 8.57(m,1H), 8.17(m,1H), 7.67˜7.03(m,4H), 4.87(s,2H), 2.97(s,3H).

EXAMPLE 27 3-Acetyl-8-chloro4-methylsulfoxy-2-quinolinone (91)

3-Acetyl-8-chloro-4-methylthio-2-quinolinone (26.7g, 0.1 mol)(3) was dissolved in 200 ml of ethyl alcohol, and herein the solution of magnesium monoperoxyphthalate (29.1g, 0.1 mol)dissolved in 150 ml of water was added dropwise at room temperature.

After raising the reaction temperature to 50° C., the reacting solution was maintained for 2hr, and then ethyl alcohol was evaporated and 500 ml water was added.

The obtained solid w as filtered and recrystallized in 100 ml of ethyl alcohol to afford the desired product (23.2g, yield: 82%).

¹ H NMR(CDCl₃): δ8.3˜7.5(m,3H), 3.1(s,3H), 2.8(s,3H).

EXAMPLE 28 3-Acetyl-6-methoxy-4-methylsulfoxy-2-quinolinone (92)

3-Acetyl-6-methoxy-4-methylthio-2-quinolinone (2.6g, 0.01 mol)(5) was dissolved in 10ml of acetic acid, and the solution was stirred at 80° C., and herein hydrogen peroxide (30% solution 2.83g, 0.025 mol) was added dropwise and stirred for 30min at 80° C.

After reacting under the above conditions, the solution was cooled and poured in 500g of ice water, and then the deposited solid was filtered and dried to obtain the desired product (2.3g, yield: 85%).

¹ H NMR(CDCl₃): δ8 7.9˜7.3(m,3H), 3.9(s,3H), 3.0(s,3H), 2.8(s,3H).

EXAMPLE 29 3-Acetyl-5,8-dichloro-4-methylsulfoxy-2-quinolinone (93)

3-Acetyl-5,8-dichloro-4-methylthio-2-quinolinone (3.0g, 0.01 mol)(4) was used, but the reaction was carried out as the above process of example 27 to obtain the desired product (2.4g, yield: 78%).

¹ H NMR(CDCl₃): δ8.0˜7.0(m,2H), 3.1(s,3H), 2.75(s,3H).

EXAMPLE 30 3-Acetyl-8-fluoro4-methylsulfoxy-2-quinolinone (97)

3-Acetyl-8-fluoro-4-methylthio-2-quinolinone (2.5g, 0.01 mol)(8) was used, but the reaction was carried out as the above process of example 27 to obtain the desired product (2.0g, yield: 79%).

¹ H NMR(CDCl₃): δ8.3˜7(m,4H), 3.05(s,3H), 2.82(s,3H).

EXAMPLE 31 3-Acetyl-6-chloro-8-trifluoromethyl-4-methylsulfoxy-2-quinolinone (98)

3-Acetyl-6-chloro-8-trifluoromethyl-4-methylthio-2-quinolinone (3.4g, 0.01 mol)(13) was used, but the reactiota was carried out as the above process of example 27 to obtain the desired product (2.9g, yield: 85%).

¹ H NMR(CDCl₃): δ2.75(s,3H), 3.0(s,3H), 8.6(d,1H), 8.0(d,1H), 11.25(s,1H).

EXAMPLE 32 3-Acetyl-4-benzylsulfoxy-8-fluoro-2-quinolinone (100)

3-Acetyl-4-benzylthio-8-fluoro-2-quinolinone (3.2g, 0.01 mol)(15) was used, but the reaction was carried out as the above process of example 27 to obtain the desired product (2.9g, yield: 87%).

¹ H NMR(CDCl₃): δ2.86(s,3H), 4.37(s,2H), 7.13˜7.47(m,8H), 8.16(s,1H).

EXAMPLE 33 3-Acetyl-8-trifluoromethyl-4-methylsulfoxy-2-quinolinone (102)

3-Acetyl-8-trifluoromethyl-4-methylthio-2-quinolin one (3.0 g, 0.01 mol)(29 ) was used, but the reaction was camed out as the above process of example 27 to obtain the desired product (2.5g, yield: 82%).

¹ H NMR(CDCl₃): 2.87(s,3H), 3.03(s,3H), 7.52˜8.78(m,3H), 11.25(s,1H)

EXAMPLE 34 3-Acetyl-8-cyano-4-methylsulfoxy-2-quinolinone (104)

3-Acetyl-8-cyano-4-methylthio-2-quinolinone (2.6g, 0.01 mol)(29) was used, but the reaction was carded out as the above process of example 27 to obtain the desired product (1.8g, yield: 68%).

¹ H NMR(CDCl₃): δ2.67(s,3H), 7.6˜8.67(m,4H).

EXAMPLE 35 3-Acetyl-5,8-dichloro- 4-(p-chloro phenyl)thio-2-quinolinone (182)

3-Acetyl-5,8-dichloro-4-methylsulfoxy-2-quinolinone (3.2g, 0.01 mol)(93 ) and p-chlorothiophenol(1.73g, 0.012 mol) were stirred at 20° C., heated for 30 min, slowly cooled to 100° C., and dissolved in 15ml of toluene.

After cooling to room temperature, the deposited crystal was filtered and dried to obtain the desired product (3.3g, yield: 83%).

¹ H NMR(CDCl₃): 7.2˜8.3(m,6H), 3.00(s,3H).

EXAMPLE 36 3-Acetyl-5,8-dichloro-4-(p-chlorophenyl)sulfoxy-2-quinolinone (184)

3 -Acetyl-5,8-dichloro-4- (p-chlorophenyl)thio-2-quinolinone (1 g, 0.0025 mol) (182) was dissolved in the mixture of 5 ml of acetic acid and hydrogen peroxide (30% solution 0.57g, 0.005 mol), and stirred for 30 min at 100° C.

The solution was poured in 50g of ice water, and then the deposited solid was filtered and dried to obtain the desired product (0.8g, yield: 73%).

¹ H NMR(DMSOd₆ -CDCl₃): δ7.2˜8.3(m,6H), 3.05(s,3H).

EXAMPLE 37 3-Acetyl-6-chloro-8-trifluoromethyl-4-(2-phenylethylamino)-2-quinolinone (223)

3-Acetyl-6-chloro-8-trifluoromethyl-4-methylsulfoxy-2-quinolinone (3.5g, 0.01 mol) and 2-phenylethylamine(1.21g, 0.01 mol) were dissolved, refluxed in 50ml of tetrahydrofuran under heating for 4hr.

After reacting, the solvent was evaporated under the reduced pressure, and then the obtained solid was dissolved in 10ml of ethylacetate under heating.

The solution was recrystallized with adding 30ml of hexane to obtain the desired product (2.57g, yield: 73%).

¹ H NMR (CDCl₃): δ11.78(brs, 1H), 8.47(d, J=2.0, 1H), 7.75(d, J=2.0, 1H), 7.75(brs, 1H), 7.33(s,5H), 3.55(m,2H), 3.08(m,2H), 2.7(s,3H).

EXAMPLE 38 3-Acetyl-6-chloro-8-trifluoromethyl-4-isopropylamino-2-quinolinone (224)

3-Acetyl-6-chloro-8-tfifluoromethyl-4-methylsulfoxy-2-quinolinone (3.5g, 0.01 mol)(13) and isopropylamine (0.6g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.52g, yield: 73%).

¹ H NMR (CDCl₃): δ11.7(s,1H), 8.58(m,1H), 7.87(m,1H), 3.77(m,J =6.5, 1H), 2.93(s,3H), 1.47(d, J=6.5, 6H).

EXAMPLE 39 3-Acetyl-6-chloro-8-trifiuoromethy- 4-cyclopentylamino-2-quinolinone (227)

3-Acetyl-6-chloro-8-trifluoromethyl-4-methylsulfoxy-2-quinolinone (3.5g, 0.01 mol) and cyclopentylamine (0.86g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.5g, yield: 67 % ).

¹ H NMR (CDCl₃): δ11.8(brs, 1H), 8.47(m,1H), 7.83(brs, 1H), 7.77(m,1H), 3.85(brs, 1H), 2.73(s,3H), 2.47˜1.38(m,8H).

EXAMPLE 40 8-Chloro-3-propionyl-4-isopropylamino-2-quinolinone (229)

8-Chloro-4-methylsulfoxy-3-propionyl-2-quinolinone (2.97g, 0.01 mol) and isopmpylamine (0.6g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.93g, yield: 71% ).

¹ HNMR (CDCl₁): δ11.78(br,1H), 8.4˜6.97(m,4H), 3.87(m,J=7.0, 1H), 3.27(q,J=8.0, 2H), 1.65(d, J=7.0, 6H), 1.17(t, J=8.0, 3H).

EXAMPLE 41 3-Acetyl-8-methyl-4-isopropylamino-2-quinolinone (230)

3-Acetyl-8-methyl-4-methylsulfoxy-2-quinolinone (2.63g, 0.01 mol) and isopropylamine (0.6g, 0.01 mol) were used, but the reaction was carded out as the above process of example 37 to obtain the desired product (2.59g, yield: 68%).

¹ H NMR (DMSO-d6): δ11.5(br. d, 1H), 8.33˜7.23(m,4H), 3.8(m, J=7.0, 1H), 2.77(s,3H), 2.4(s,3H), 1.45(d,J=7.0,6H).

EXAMPLE 42 3-Acetyl-6-chloro-8-trifluoromethyl-4-(p-fluorophenethyl amino)-2-quinolinone (227)

3-Acetyl-6-chloro-8-trifluoromethyl-4-methylsul foxy-2-quinolinone (3.5g, 0.01 mol), p-fluorophenethylamine hydrochloride(1.76g, 0.01 mol) and triethylamine (1.1g, 0.01 mol) were used as the above process of example 37, and the solvent was evaporated under the reduced pressure.

The residue was dissolved in 50 ml of ethylacetate, washed with 50 ml of water, dried with magnessium sulfate, and then the solvent was evaporated.

The obtained solid was dissolved in 10 ml of ethyl acetate, and crystallized by adding 30 ml of hexane to afford the desired product (2.25g, yield: 53%).

¹ H NMR (CDCl₃): δ2.7(s,3H), 2.97˜3.16(t,J=6.4, 2H), 3.47˜3.77(m,2H), 6.93˜8.47(m,7H), 11.73(s,1H).

EXAMPLE 43 3-Acetyl-8-fluoro-4-(1-methoxy-2-propylamino)-2-quinolinone (249)

3-Acetyl-8-fluoro-4-methylsulfoxy-2-quinolinone (2.67g, 0.01 mol) and 1-methoxy-2-propylamine(0.88g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.53g, yield: 87%).

¹ H NMR (CDCl₃): δ1.5(d,3H), 2.8(s,3H), 3.7˜3.9(m,3H), 3.6(s,3H), 7.2˜8.3(m, 4H).

EXAMPLE 44 3-Acetyl-6-chloro-8-trifluoromethyl-4-ethylamino-2-quinolinone (251)

3-Acetyl-6-chloro-8-trifluoromethyl-4-methylsulfoxy-2-quinolinone (3.5g, 0.01 mol) and ethylamine(70 wt % solution; 0.65g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.52g, yield: 76%).

¹ H NMR (CDCl₃): δ1.37˜1.6(t,J=8, 3H), 2.73(s,3H), 3.23˜3.67(m,2H), 7.77˜8.47(m,3H), 11.57(s,1H).

EXAMPLE 45 3 -Acetyl- 8- fl uo ro-4- (2 -methyl cyclohexylamino )-2-quinolinone (256)

3-Acetyl-8-fiuoro-4-methylsulfoxy-2-quinolinone (2.67g, 0.01 mol) and 2methylcyclohexylamine(1.13g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.1g, yield: 66%).

¹ H NMR (CDCl₃): δ1.0˜1.5(m,12H), 2.6(s,3H), 3.9(m,1H), 7.1˜8.4(m,3H).

EXAMPLE 46 3-Acetyl-8-trifluoromethyl-4-(a -methylbenzylamino)-2-quinolinone (260)

3-Acetyl-8-trifluoromethyl-4-methylsulfoxy-2-quinolinone (3.17 g, 0.01 mol) and α-methylbenzylamine (1.21 g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.43g, yield: 65%).

¹ H NMR (CDCl₃): δ1.63˜1.83 (d,J=7, 3H), 2.8(s,3H), 4.57˜4.77(m,1H), 7.23˜8.6(m,9H), 12.2(s,1H).

EXAMPLE 47 3-Acetyl-8-chloro-4-(p-chlorobenzylamino)-5-nitro-2-quinolinone (308)

3-Acetyl-8-chloro-4-methylsulfoxy-5-nitro-2-quinolinone (3.28g, 0.01 mol ) and p-chlorobenzylamine (1.42g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.32g, yield: 57%).

¹ H NMR (DMSO-d₆): δ8 11.9(m,1H), 8.43(brs, 1H), 7.8(d,J=9.0, 1H), 7.5(s,4H), 7.3(d,J=9.0, 1H), 4.9(d,J=6.0, 2H), 2.7(s,3H).

EXAMPLE 48 3-Acetyl-6,8-dichloro-4-(2-methylchclohexylamino)-2-quinolinone (311 )

3-Acetyl-6,8-dichloro-4-methylsulfoxy-2-quinolinone (3.18g, 0.01 mol) and 2-methylcyclohexylamine (1.13g, 0.01 mol) were used, but the reaction was carried out as above process of example 37 to obtain the desired product (2.68g, yield: 73%).

¹ H NMR (CDCl3): δ12.0(m,1H), 8.2(d,J=2.0, 1H), 7.9(brs, 1H), 7.6(d,J=2.0, 1H), 3.0(m,1H), 2.8(s,3H), 1.0˜2.5(m,9H), 1.0˜1.2(m,3H).

EXAMPLE 49 3-Acetyl-7-t-butyl-4-cyclobutylamino-2-quinolinone (377)

3-Acetyl-7-t-butyl-4-methylsulfoxy-2-methylsulfoxy-2-quinolinone (3.05g, 0.01 mol) and cyclobutylamine (0.71g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.6g, yield: 83 % ).

¹ H NMR (CDCl₃ ): δ11.4(m,1H), 8.3˜8.4(d,1H), 7.2˜7.7(m,2H), 2.9(s,3H), 1.5˜2.9(m,4H), 1.2(s,9H), 0.9˜1.1(m,2H).

EXAMPLE 50 3-Acetyl-8-ethyl-4-cyclopentylamino-2-quinolinone (400)

3-Acetyl-8-ethyl-4-methylsulfoxy-2-quinolinone (2.77g, 0.01 mol) and cyclopentylamine (0.86g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.15g, yield: 72%).

¹ H NMR (CDCl₃): δ11.6(m,1H), 8.1(d,J=6.0, 1H), 7.4˜7.1(m,3H), 3.8(m,1H), 2.8(s,3H), 2.7(m,2H), 2.1˜1.5(m,8H), 1.4(t,J=6.0, 3H).

EXAMPLE 51 3-Acetyl-6-chloro-8-methyl-4-(p-fluorophenethylamino)-2-quinolinone (420)

3-Acetyl-6-chloro-8-methyl-4 -methylsulfoxy -2-quinolinone (2.98 g, 0.01 mol) and p-fluorophenethylamine hydrochloride (1.76g, 0.01 mol) were used, but the reaction was carried out as the above process of example 42 to obtain the desired product (2.9g, yield: 71%).

¹ H NMR (DMSO-d₆): δ11.5(m,1H), 8.3(s,1H), 7.9(s,1H), 7.6˜6.8(m,5H), 3.77(m,2H), 3.0(t,J=7.0, 2H), 2.6(s,3H), 2.4(s,3H).

EXAMPLE 52 3-Acetyl-5,8-dichloro-4-(N-morpholino)-2-quinolinone (513)

3-Acetyl-5,8-dichloro-4-methylsulfoxy-2-quinolinone (3.18g, 0.01 mol) and morpholine (0.87 g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.56g, yield: 75%).

¹ H NMR (DMSO-d₆): δ6.7˜7.3(m,3H), 2.9˜3.3(m, 8H), 2.3(s,3H).

EXAMPLE 53 3-Acetyl-5,7-dimethyl-4-(β-methylphenethylamino))-2-quinolinone (533)

3-Acetyl-5,7-dimethyl-4-methylsulfoxy-2-quinolinone (2.77g, 0.01 mol)and β-methylphenethylamine (1.35g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain hhe desired product (2.96g, yield: 85%).

¹ H NMR (DMSO-d₆): δ11.6(m,1H), 7.2(s,5H), 6.7˜7.1 (d,2H), 3.5(m,2H), 3.2(m,1H), 2.7(s,3H), 2.6(s,3H), 2.2(s, 3H), 1.3(d,3H).

EXAMPLE 54 3-Acetyl-4-sec-butylamino-8-isopropyl-2-quinolinone (543)

3-Acetyl-4-methylsulfoxy-8-isopropyl-2-quinolinone (2.91g, 0.01 mol) and sec-butylamine (0.73g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.7g, yield: 90%).

¹ H NMR (CDCl₃): δ11.6(m,1H), 8.2(d,J=8.0, 1H), 7.7˜7.1(m,3H), 3.5(m,1H), 2.9(m,1H), 2.8(s,3H), 1.7(m,2H), 1.4(m,9H), 1.1(t,J=6.0, 3H).

EXAMPLE 55 3-Acetyl-4-(β-methylphenethylamino)-8-phenyl-2-quinolinone (565)

3-Acetyl-4-methylsulfoxy-8-phenyl-2-quinolinone (3.25g, 0.01 mol) and β-methylphenethylamine (1.35g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (3.29g, yield: 83%).

¹ H NMR (DMSO-d₆): δ11.3(m,1H), 8.3(brs, 1H), 8.3˜8.0(m,1H), 7.8˜6.9(m,12H), 3.3(m,2H), 3.03(m,1H), 2.6(s,3H), 1.23(d,J=7.0, 3H).

EXAMPLE 56 3-Acetyl-4-allylamino-8-propyl-2-quinolinone (603)

3-Acetyl-4-allylamino-8-propyl-2-quinolinone (2.91g, 0.01 mol) and allylamine (0.57g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.31g, yield: 75%).

¹ H NMR (CDCl₃): δ11.6(m,1H), 8.1(d,J=8.0, 1H), 7.7˜7.1(m,3H), 6.0˜5.3(m,3H), 4.1(brs,2H), 2.8(s,3H), 2.6(t,J=7.0, 2H), 1.5(m,2H), 1.0(t,J=6.0, 3H).

EXAMPLE 57 3-Acetyl-4-allylamino-8-chloro-6-methyl-2-quinolinone (611)

3-Acetyl-8-chloro-6-methyl-4 -methylsulfoxy -2-quinolinone (2.97 g, 0.01 mol) and allylamine (0.57g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.38g, yield: 82%).

¹ H NMR (DMSO-d₆): δ11.6(m,1H), 8.2(s,1H), 7.4˜7.7(d,2H), 5.0˜6.1 (m,3H), 3.1 (t,2H), 2.5(s,3H), 2.2(s,3H).

EXAMPLE 58 3-Acetyl-4-allylamino-5-chloro-6-methyl-2-quinolinone (632)

3-Acetyl-5-chloro-6-methyl-4-methylsulfoxy-2-quinolinone (2.69g, 0.01 mol) and allylaminc (0.57g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.23g, yield: 77%).

¹ NMR (CDCl₃): δ11.4(m,1H), 7.1˜7.6(m,3H), 5.1˜6.2(m,3H), 4.0˜4.2(m,2H), 2.6(s,3H), 2.4(s,3H).

EXAMPLE 59 3-Acetyl-8-chloro-4-(p-chlorophenethylamino-5-methyl-2-quinolinone (656)

3-Acetyl-8-chloro-5-methyl-4-methylsulfoxy-2-quinolinone (2.97 g, 0.01 mol) and p-chlorophenethylamine (1.56g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (3.1 lg, yield: 80%).

¹ H NMR (DMSO-d₆): δ11.6(m,1H), 8.7(s,1H), 7.7(s,4H), 7.1˜7.9(m,2H), 3.9(q,2H), 3.2(t,2H), 2.9(s,3H), 2.7(s,3H).

EXAMPLE 60 3-Acetyl-4-isoamylamino-6-fluoro-8-chloro-2-quinolinone (673)

3-Acetyl-8-chloro-6-fluoro-4-methylsulfoxy-2-quinolinone (3.02g, 0.01 mol) and isoamylamine (0.87g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.79g, yield: 86% ).

¹ H NMR (CDCl₃): δ11.6(m,1H), 8.0˜7.8(m,2H), 7.4(dd, J=8.0, 2.0, 1H), 3.4(m,2H), 2.8(s,3H), 1.7(m,3H), 0.9(d,J=6.0, 6H).

EXAMPLE 61 3-Acetyl-4-isobutylamino-5-trifluoromethyl-8-methoxy-2-quinolinone (682)

3-Acetyl-5- trifluoromehyl-8-methoxy-4-methylsulfoxy-2-quinolinone (3.4 7g, 0.01 mol) and isobutylamine (0.73g, 0.01 mol) were used, but the reaction was carried out as the above process of example 37 to obtain the desired product (2.46g, yield: 69%).

¹ H NMR (DMSO-d₆): δ11.1(m,1H), 8.5(brs,1H), 7.2˜7.7(m,2H), 4.2(s,3H), 3.0˜3.6(m,2H), 2.6(s,3H), 1.8˜2.3(m,1H), 1.1 (d,J=6.0, 6H).

The fungicidal activities of 2-quinolinone derivatives(I) according to the present invention prepared by the above examples were tested by following Tests; wherein all the test chemicals were readily dispersed in a standard formulation of acetone in water and surfactant. Five ml of acetone containing 12.5 mg of the chemical was diluted in 45 ml of Tween 20 solution (250 ppm). Fifty ml of this chemical solution was sprayed to plants on the ramtable at the same time. All replicates of plants tested for fungicidal activity against 6 plant diseases were two pots, respectively.

TEST 1 Fungicidal Test for Rice Blast (RCB )

Evaluation of activity against blast was done with rice plants in the 2 leaf stage, grown in 5 cm pots with a foliage spray. Fifty ml test material was sprayed on the foliage. After the spray deposit had dried, the plants were inoculated with a suspension of conidia in water (1×10⁶ spores/ml) and placed in a dew chamber at 25° C. for 24 hrs. For inoculum preparation, rice blast fungus was incubated on rice polish agar medium at 26° C. for 2 weeks, and then scratched airial mycelia with rubber and irradiated with near UV light for 2 days. The plants were then held in lighted gowth chamber (26°±2° C., 85%) for an additional 5 days, and rated on the disease severity.

TEST 2 Fungicidal Test for Rice Sheath Blast (RSB)

Rice plants in the 3 leaf stage were sprayed with 5 ml of chemical solution on the turntable. One day after drying, treated plants were inoculated by injecting inoculum, incubated in wileat bran medium at 25° C. for 7 days, macerated into the mixer at the base of the rice plants. Those were moved to a lighted dew chamber at 28° C.and then held for 5 days. The disease severity of each pot was examined and compared to the standard rating diagram.

TEST 3 Fungicidal Test for Cucumber Gray Mold (CGM)

Cucumber plants grown in the fast leaf stage were sprayed with 50 ml of chemical solution while those were rotated on the mintable. After the spray deposit had dried for one day, the treated foliage of cucumber was inoculated with conidia (1×10⁶ spores/ml) of B. cinerea incubated on potato dextrose agar medium at 25° C. for 15 days by leaf spray all tour sides of plants until just before runoff and then placed in 20° C. dew chamber for 4˜5 days. The disease rating was made by examining the applied plants and comparing the percent disease on a leaf to the standard rating diagram.

TEST 4 Fungicidal Test for Tomato Late Blight (TLB)

Tests were made onto tomato plants grown in 5 cm polyvinyl pots for 14 days by leaf spray. The foliage is sprayed to run off with a test chemical while the plant rotated on a turntable. After the spray deposit dried for one day, the treated plants were inoculated by spraying then with a suspension of zoosporangia (1×10⁵ zoosporangia/ml) incubated on V-8 juice agar medium at 20° C. for 2 weeks and then placed in a dew chamber at 18° C. for 48 hrs. Four days after inoculation, disease ratings were made on a investigation of the disease severity.

TEST 5 Fungicidal Test for Wheat Leaf Rust (WLR)

Tests were made on wheats (cultivar; Chokwang) grown in polyvinyl pots (diameter; 5 cm) for 7 days by foliage spray. The first leaf was sprayed while plaints were rotating on a turntable with 5 ml of a chemical solution. After the spray deposit dried, plants were dusted with a uredospores colonied on the second leaf of wheat and placed in a moist chamber at 20° C. for 24 hours. One day after inoculation, plant were moved to the plant growth chamber (20° C., 70% RH) for inducing the disease. The fungicidal effect of the applied chemicals was investigated on the disease severity of wheats after 10 days.

TEST 6 Fungicidal Test for Barley Powdery Mildew (BPM)

The barley powdery mildew is an obligately parasitic fungus that must be transferred directly from infected plants to healthy plants in a relatively dry environment. The host plants (cultivar; Allbori) sowed in polyvinyl pot(diameter; 5 cm) were grown in a greenhouse for 7 days. Healthy young barley with fully expanded primary leaf was spray with a suspension of a test material. One day after drying, the applied plants were dusted with conidia of Erysiphe graminis formed on the primary leaf of barley. The inoculated plants were placed in a plant growth chamber at 22°˜24° C. and then induced the powdery mildew. The disease severity was rated after 7 day inoculation.

Fungicidal activity of test chemical against the above 6 plant diseases was indicated with control value calculated bv below formula to list the result as below Table 4. ##EQU1##

                  TABLE 4                                                          ______________________________________                                         Fungicidal effects for 2-quinolinone                                           Comp. No.                                                                               RCB     RSB     CGM   TLB   WLR   BPM                                 ______________________________________                                          13      100     80      --    --    100   58                                   18      97      --      --    --    --    --                                   19      84      65      --    97    --    --                                   33      96      --      --    --    100   100                                  34      89      --      --    --    100   84                                   35      100     100     --    --    --    --                                   38      96      68      --    --    100   --                                   39      14      45      99    94    29    28                                   49      95      74      42    78    99    49                                   55      0       32      92    0     0     51                                   75      100     100     0     0     99    75                                  106      99      95      57    100   53    10                                  107      94      20      93    99    60    9                                   108      97      67      95    100   53    9                                   111      99      95      95    97    53    10                                  112      99      95      95    97    53    16                                  118      0       30      90    56    0     0                                   120      91      60      95    92    53    0                                   129      0       37      98    38    0     0                                   131      0       16      99    47    53    23                                  137      96      53      94    94    27    0                                   152      99      95      89    60    33    58                                  159      93      90      66    0     91    69                                  165      99      90      83    31    67    0                                   176      99      32      38    73    0     0                                   181      99      63      31    57    75    95                                  183      94      74      0     50    75    18                                  189      94      100     0     0     100   100                                 190      86      90      91    62    45    0                                   191      100     85      42    30    10    33                                  192      100     90      100   18    43    95                                  193      100     95      40    70    100   70                                  194      99      99      81    20    100   55                                  195      100     99      100   0     99    56                                  196      100     86      45    100   42    0                                   197      99      92      0     7     100   83                                  199      99      52      73    61    8     53                                  200      96      52      21    72    56    4                                   204      72      81      0     0     100   100                                 205      100     21      76    98    81    54                                  206      100     91      61    0     100   71                                  211      100     75      21    92    38    8                                   215      84      13      19    0     67    97                                  219      0       20      95    6     53    0                                   222      91      26      69    24    27    0                                   224      100     100     --    --    67    89                                  226      100     --      --    48    --    --                                  228      99      --      --    91    --    --                                  231      100     --      --    --    --    97                                  235      87      11      --    89    --    --                                  236      100     100     35    89    --    --                                  237      --      69      --    93    93    --                                  238      --      100     --    47    98    --                                  239      --      --      --    89    --    --                                  242      100     100     100   --    93    76                                  247      97      --      --    96    --    --                                  251      100     100     --    --    96    --                                  253      --      --      94    --    --    --                                  257      --      --      77    95    --    --                                  259      99      --      --    --    --    --                                  267      71      --      95    35    14    42                                  268      0       0       92    19    0     53                                  272      100     --      66    100   --    --                                  279      99      35      68    87    53    2                                   282      7       0       98    97    0     35                                  308      0       53      15    98    --    --                                  310      0       13      90    37    27    31                                  313      98      53      58    95    60    11                                  336      0       0       100   21    0     13                                  368      18      0       93    0     0     2                                   404      0       0       59    0     99    100                                 407      57      0       38    95    67    29                                  435      93      71      48    91    93    0                                   475      0       10      95    48    67    43                                  476      0       95      67    11    0     61                                  506      0       35      94    65    0     0                                   540      0       20      94    55    0     0                                   542      0       30      94    84    0     0                                   545      0       95      42    82    53    1                                   550      0       58      97    63    0     0                                   608      7       75      82    93    9     0                                   609      0       15      92    21    0     0                                   708      93      28      68    46    0     0                                   709      14      28      92    3     0     0                                   711      0       50      94    13    0     17                                  713      7       5       95    77    0     39                                  715      0       0       100   28    27    4                                   718      96      60      13    78    27    5                                   720      93      30      38    81    53    20                                  721      99      95      59    83    80    5                                   736      100     100     60    71    53    19                                  737      98      80      0     76    82    14                                  745      0       5       92    59    0     16                                  746      0       30      94    71    0     0                                   759      0       10      96    76    0     46                                  761      99      95      0     60    53    95                                  765      0       11      95    36    0     0                                   791      93      61      40    46    0     17                                  792      98      11      81    94    27    29                                  793      91      15      100   47    53    45                                  797      99      60      100   96    53    4                                   798      97      20      13    35    27    32                                  801      99      70      0     65    75    31                                  802      98      70      72    79    68    42                                  803      100     95      99    50    67    24                                  804      99      68      100   29    53    58                                  805      100     95      80    57    60    61                                  806      100     79      56    36    27    14                                  807      99      95      69    57    53    0                                   808      99      95      50    43    53    10                                  809      99      58      71    53    60    2                                   810      99      21      81    73    53    24                                  813      99      37      56    24    33    14                                  830      0       0       93    23    0     20                                  831      0       0       100   46    0     15                                  837      96      60      72    81    36    0                                   839      0       35      96    87    45    15                                  841      57      90      91    86    77    9                                   846      0       0       98    77    0     0                                   853      91      85      78    15    0     98                                  862      99      5       77    0     27    36                                  869      0       100     24    0     96    95                                  870      100     83      3     56    87    0                                   871      100     63      12    73    92    33                                  876      97      33      21    53    81    62                                  877      100     8       15    62    63    53                                  878      100     96      24    0     82    18                                  905      26      0       0     98    96    23                                  908      0       0       0     95    64    5                                   915      100     82      28    85    81    23                                  916      100     82      36    81    76    15                                  928      23      75      67    25    99    61                                  929      90      90      63    0     100   92                                  932      86      95      20    15    96    91                                  933      100     75      40    0     33    70                                  936      100     35      7     25    91    46                                  937      100     15      64    32    27    39                                  939      100     35      14    96    27    81                                  944      50      85      0     0     96    99                                  946      14      90      0     0     100   99                                  947      21      0       24    0     100   97                                  949      94      60      23    0     53    97                                  ______________________________________                                    

As the result of the above Table 4, the com pounds according to the present invention have a high protective effect against CGM and TLB, and also RCB.

The insecticidal activity of the compounds of the formula(I) according to the present invention was tested as following Tests 7˜10.

The Primary Screening(PRI) is designed to detect initial pest control activity of experimental compounds. The types of activity assayed are acute toxicity, and growth disruption. The bioassay are designed to detect contact and ingestion activity.

The stage tested are as follows: adult brown planthopper(BPH), green peach aphid(GPA), and two-spotted spider mite (TSSM), and 3rd instar diamondback moth(DBM).

All experimental compounds are formulated in a 10: 90 (acetone: water), Triton X-100 100ppm solution at a single, unreplicated rate of 500 ppm. Formulated compounds are applied to the test species with the individual application methods respectively.

TEST 7 Insecticidal Test for Brown Plant Hopper (BPH)

Root parts of six rice seddlings (cultivar: Dongjin; 5-6 cm in length; 5-10 day old) are rolled with cotton wool pads and rice seedlings are put into the glass test robes(φ3×15 cm) containing 2 ml water. Three to five day-old adult BPH (20 individuals) are collected from rearing cages by an aspirator, and placed into test robes.

Test chemicals are dissolved in 5 ml acetone(100%), and formulated to the proper concentration in Triton X- 100 (100ppm), then sprayed onto the BPH directly. The test tubes are covered with nylon cloth and held in an incubator at 25° C. Insect mortalities are recorded at 24 and 48 hours after treatment.

TEST 8 lnsecticidal Test for Green Peach Aphid (GPA)

Excised tobacco leaf disks (5.5 cm in diameter) are dipped into the prepared test chemical solutions (30 sec) and taken out. After drying (30 min), leaf disks are placed in the petridishes (φ5.5×2 cm) and apterous female adult GPAs (20 individuals) are enclosed. All petridishes are covered and held in an incubator at 25° C. Insect mortalities are recorded at 24 and 48 hours after treatment.

TEST 9 Insecticidal Test for Two-Spotted Spider Mite (TSSM)

Excised kidney bean leaf disks (2.5 cm in diameter) are placed on water saturated cotton wool pads fitted into petridishes (φ5.5×2 cm). Female adult TSSMs (30 individuals) are placed on leaf disks, and prepared test chemicals are sprayed. The petridishes are covered and held in an incubator at 25° C. Mite mortalities are recorded at 24 and 48 hours after teatment.

TEST 10 Insecticidal Test for Diamond-Back Moth (DBM)

Test chemicals axe dissolved in 5ml acetone (100%), then formulated to the proper concentration in Triton X- 100 (100 ppm). Excised cabbage leaf disks(5 cm in diameter) are dipped into the solution (30 sec) and taken out. After drying (30 min), leaf disks are placed in the petridishes (φ5×1 cm) and 3rd instar DBM larvae (10 individuals) are enclosed. All petridshes are covered and held in an incubator at 25° C. Insect mortalities are recorded at 24 and 48 hours after treatment.

The mortality (%) of test chemical against the above plant diseases was calculated by the below fomula to list the result as the following Table 5. ##EQU2##

                  TABLE 5                                                          ______________________________________                                         Insecticidal effects for 2-quinolinone (I)                                     Comp. No.   BPH    GPA       DBM   TSSM                                        ______________________________________                                          13         --     --        --    100                                          28         --     --        90    --                                           29         20     0         90    100                                          30         10     0         20    100                                          33         0      25        40    100                                          34         5      75        60    100                                          38         0      30        80    100                                         224         10     0         100    63                                         241         0      0         100    0                                          242         0      0         80    100                                         245         0      0         90    100                                         307         0      10        100    7                                          404         0      0         100   100                                         460         0      0         100    0                                          ______________________________________                                    

As the result of the above Table 5, the compounds of the formula(I) according to the present invention have selectively good activity against diamond-back moth and two-spotted spider mite. 

What is claimed is:
 1. 2-Quinolinone derivatives having the following formula (I) ##STR754## wherein, R₁, R₂, R₃ and R₄ are independently hydrogen, halogen, C₁ -C₁₀ alkyl, C₁ -C₃ haloalkyl, C₁ -C₈ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃ haloalkylthio, NO₂, CN, alkoxy carbonyl, phenyl, phenoxy, benzenesulfonyl, benzyl, or morpholine;R₅ is C₁ -C₆ alkyl, C₃ -C₆ cycloalkyl, phenyl, benzyl or phenylthio methyl; and X is S(O)nR₆, OR₉ or NAB;wherein, n is 0 or 1; R₆ is R₇ or R₈, and R₇ is C₁ -C₆ alkyl, C₁ -C₃ haloalkyl, benzyl or benzyl substituted with a C₁ -C₄ alkyl, C₁ -C₃ alkoxy, one or two halogen groups, or trifluoromethyl, and R₈ is phenyl, phenyl substituted with a halogen, or benzyl; R₉ is C₂ -C₅ alkyl, C₅ -C₆ cycloalkyl, phenyl or phenyl substituted with a halogen; A and B are combined together with the nitrogen atom to form a saturated or unsaturated 5 or 6-membered cyclic ring or benzofused 5- or 6-membered cyclic ring, or a saturated or unsaturated 5 or 6-membered cyclic ring including an additional hetero atom selected from O or N, or a saturated or unsaturated 5 of 6-membered cyclic ring, substituted with C₁ -C₃ alkyl, or one of A and B is H and the other is R₁₀ or Z--Ar;and then, R₁₀ is saturated C₁ -C₁₀ alkyl, propenyl, C₃ -C₆ cycloalkyl which includes a hetero atom selected from O, S or N or C₃ -C₆ cycloalkyl substituted with C₁ -C₃ alkyl or alkoxycarbonyl, C₁ -C₃ haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl, Ar, pyridyl, pyridyl substituted with a halogen, one or two C₁ -C₃ alkyl groups, or C₁ -C₃ alkoxy, pyrimidyl or pyrimidyl substituted by one or two C₁ -C_(]) alkyl, C₁ -C₃ alkoxy, or one or two C₁ -C₃ alkyl and C₁ -C₃ alkoxy; Z is C₁ -C₄ alkyl chain, C₁ -C₄ alkyl chain containing cyclopropylene ring, or C₁ -C₄ alkyl chain substituted with C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ hydroxyalkyl or phenyl; and Ar is C₃ -C₆ cycloalkyl, C₃ -C₆ cycloalkyl including a nitrogen atom, or pyridyl, or a phenyl group of the following formula(II) ##STR755## wherein, R₁₁, R₁₂, R₁₃, R₁₄ and R15 are independently H, halogen, C₁ -C₆ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, phenyl, phenoxy, phenylthio, CN, NO₂, NH₂, or SO₂ NH₂.
 2. Fungicides including a fungicidal effective amount of 2-quinolinone derivatives having the following formula (I) as an effective ingredient ##STR756## wherein, R₁, R₂, R₃, R₄, R₅ and X are as defined in the above claim
 1. 3. Insecticides including an insecticidal effective amount of 2-quinolinone derivatives having the following formula (I) as an effective ingredient ##STR757## wherein, R₁, R₂, R₃, R₄, R₅ and X are as defined in the above claim
 1. 4. A process for preparing 2-quinolinone derivatives of the following formula(Ia) by thermally cyclizing ketenedithioacetal α-anilide of the following formula(HI). ##STR758## wherein, R₁, R₂, R₃, R₄, R₅ and R₇ are respectively as defined in the above claim
 1. 